U.S. patent number 5,085,688 [Application Number 07/607,956] was granted by the patent office on 1992-02-04 for certain 2-(2-chloro-3-alkoxy-4-substituted benzoyl)-5-methyl-5-1,3-cyclohexanediones as herbicides.
This patent grant is currently assigned to ICI Americas Inc.. Invention is credited to Gary W. Kraatz, William J. Michaely.
United States Patent |
5,085,688 |
Michaely , et al. |
* February 4, 1992 |
Certain 2-(2-chloro-3-alkoxy-4-substituted
benzoyl)-5-methyl-5-1,3-cyclohexanediones as herbicides
Abstract
Herbicidal compounds of the formula ##STR1## wherein R.sub.3 is
methoxy or ethoxy; and R.sub.4 is bromine, methylsulfonyl or
ethylsulfonyl and their salts.
Inventors: |
Michaely; William J. (Richmond,
CA), Kraatz; Gary W. (San Jose, CA) |
Assignee: |
ICI Americas Inc. (Wilmington,
DE)
|
[*] Notice: |
The portion of the term of this patent
subsequent to October 25, 2005 has been disclaimed. |
Family
ID: |
27494714 |
Appl.
No.: |
07/607,956 |
Filed: |
November 1, 1990 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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128128 |
Feb 23, 1988 |
5006158 |
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880370 |
Jun 30, 1986 |
4780127 |
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772593 |
Sep 5, 1985 |
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634408 |
Jul 31, 1984 |
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587331 |
Mar 7, 1984 |
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532869 |
Sep 16, 1983 |
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464251 |
Feb 9, 1983 |
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361658 |
Mar 25, 1982 |
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Current U.S.
Class: |
504/348; 568/31;
568/329 |
Current CPC
Class: |
A01N
35/06 (20130101); C07C 45/72 (20130101); C07C
205/45 (20130101); C07C 49/84 (20130101); C07C
49/813 (20130101) |
Current International
Class: |
A01N
35/06 (20060101); A01N 35/00 (20060101); C07C
49/813 (20060101); C07C 49/84 (20060101); C07C
49/00 (20060101); C07C 45/00 (20060101); C07C
45/72 (20060101); A01N 035/4 (); C07C
049/303 () |
Field of
Search: |
;568/329,31
;71/123,103 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0007243 |
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Jan 1980 |
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EP |
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0017195 |
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Oct 1980 |
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EP |
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0090262 |
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Oct 1983 |
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EP |
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137963 |
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Apr 1985 |
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EP |
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0162336 |
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Nov 1985 |
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EP |
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13750-76 |
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Jul 1974 |
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JP |
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662543 |
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May 1979 |
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SU |
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2110673 |
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Jun 1983 |
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GB |
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Other References
Akhrem et al., "A New Simple Synthesis of 2-Acylcyclohexane-1,
3-Diones", Communications, Georg Thieme Publishers, 1978, pp.
925-927. .
Chemical Abstracts, vol. 85 (1976), Sawaki et al.,
"2-(Amino-Methylene)-1,3-Cyclohexandiones", p. 423, Abstract
#85:5280f..
|
Primary Examiner: Brust; Joseph Paul
Attorney, Agent or Firm: Baker; Edwin H.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation application of Ser. No.
07/128,128, filed Feb. 23, 1988, now U.S. Pat. No. 5,006,158 which
is a divisional application of Ser. No. 06/880,370, filed June 30,
1986, now U.S. Pat. No. 4,780,127 which is a continuation-in-part
applicattion of Ser. No. 772,593, filed Sept. 5, 1985, now
abandoned; which in turn is a contination-in-part application of
Ser. No. 634,408, filed July 31, 1984, now abandoned; which in turn
is a contination-in-part application of Ser. No. 587,331, filed
Mar. 7, 1984, now abandoned; which in turn is a
continuation-in-part application of Ser. No. 532,869, filed Sept.
16, 1983, now abandoned; which in turn is a continuation-in-part
application of Ser. No. 464,251, filed Feb. 9, 1983, now abandoned;
which in turn is a continuation-in-part application of Ser. No.
361,658, filed Mar. 25, 1982, now abandoned.
Claims
We claim:
1. Compounds having the structural formula ##STR96## wherein
R.sub.3 is methoxy or ethoxy and
R.sub.4 is bromine, methylsulfonyl or ethylsulfonyl and their
salts.
2. A method of controlling undesireable vegetation comprising
applying to the area where control is desired an herbicidally
effective amount of a compound having the structural formula
##STR97## wherein R.sub.3 is methoxy or ethoxy and
R.sub.4 is bromine, methylsulfonyl or ethylsulfonyl and their
salts.
3. An herbicidal composition comprising an herbicidally effective
amount of a compound having the structural formula ##STR98##
wherein R.sub.3 is methoxy or ethoxy and
R.sub.4 is bromine, methylsulfonyl or ethylsulfonyl and their salts
and an inert carrier therefor.
Description
BACKGROUND OF THE INVENTION
Compounds having the structural formula ##STR2## wherein X can be
alkyl, n can be 0, 1, or 2, and R.sub.1 can be phenyl or
substituted phenyl are described in Japanese Patent Application
84632-1974 as being intermediates for the preparation of herbicidal
compounds of the formula ##STR3## wherein R.sub.1, X, and n are as
defined above and R.sub.2 is alkyl, alkenyl, or alkynyl.
Specifically taught herbicidal compounds of this latter group are
those where n is 2, X is 5,5-dimethyl, R.sub.2 is allyl and R.sub.1
is phenyl, 4-chlorophenyl or 4-methoxyphenyl.
The precursor intermediates for these three specifically taught
compounds have no or almost no herbicidal activity.
DESCRIPTION OF THE INVENTION
Embodiment A of this invention relates to certain novel
2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The
compounds of this embodiment have the following structural formula
##STR4## wherein
R and R.sup.1 are hydrogen, C.sub.1 -C.sub.4 alkyl, preferably
methyl or isopropyl, R.sup.a OC(O)-, where R.sup.a is C.sub.1
-C.sub.4 alkyl; most preferably R and R.sup.1 are hydrogen;
R.sup.2 is chlorine, bromine, iodine or C.sub.1 -C.sub.4 alkoxy,
preferably methoxy; most preferably R.sub.2 is chlorine, bromine or
methoxy;
R.sup.3, R.sup.4 and R.sup.5 independently are hydrogen or an
aliphatic group, preferably: (1) hydrogen; (2) halogen, preferably
chlorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5)
trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4
haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n --
wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl,
C.sub.1 -C.sub.4 haloalkyl, phenyl, benzyl, --NR.sup.d R.sup.e
wherein R.sup.d and R.sup.e independently are hydrogen or C.sub.1
-C.sub.4 alkyl; and n is the integer 0, 1 or 2, preferably 2;
##STR5## wherein R.sup.c is C.sub.1 -C.sub.4 alkyl and R.sup.j is
hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl; (11) R.sup.f
C(O) wherein R.sup.f is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1
-C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy; (12) --NR.sup.g
R.sup.h wherein R.sup.g and R.sup.h independently are hydrogen or
C.sub.1 -C.sub.4 alkyl; or less preferably (13) R.sup.3 and R.sup.4
together can form a ring structure with two adjacent carbon atoms
of the phenyl ring.
R.sup.3 and R.sup.4 can also be (14) C.sub.3 -C.sub.5 alkenyloxy
(thio) optionally substituted, preferably with halogen or (15)
C.sub.3 -C.sub.5 alkynyloxy (thio), optionally substituted,
preferably with halogen.
Most preferably, R.sup.3 is chlorine, hydrogen, dimethylamino or
methoxy. Preferably, R.sup.4 is hydrogen, chlorine, nitro, SO.sub.2
CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2 or trifluoromethyl.
Preferably, R.sup.5 is hydrogen.
Embodiment A' of this invention is an herbicidal composition
comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione
and an inert carrier threfor. Preferably, the 2-position of the
benzoyl moiety is substituted with chlorine, bromine, iodine or
C.sub.1 -C.sub.4 alkoxy; more preferably chlorine, bromine or
methoxy; most preferably chlorine. The 5-position of the
1,3-cyclohexanedione moiety can be substituted with one or two
C.sub.1 -C.sub.4 alkyl groups, preferably methyl, although such a
substitution is not preferred.
The compounds of Embodiment A of this invention can have the
following four structural formulae because of tautomerism: ##STR6##
wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as
defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by any base to
give a salt having an anion of the following four resonance forms:
##STR7## wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5
are as defined above.
Examples of cations of these bases are inorganic cations such as
alkali metals, e.g. lithium, sodium, and potassium, alkaline earth
metals, e.g. barium, magnesium, calcium and strontium or organic
cations such as substituted ammonium, sulfonium or phosphonium
wherein the substituent is an aliphatic or aromatic group.
In the above description of the compounds of this invention, alkyl
and alkoxy include both straight and branched configurations; for
example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, and tert-butyl.
Embodiment B of this invention relates to certain novel
2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The
compounds of this embodiment have the following structural formula
##STR8## wherein
R.sup.10 is C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 -C.sub.4,
more preferably methyl;
R.sup.11 is hydrogen or C.sub.1 -C.sub.6 alkyl, preferably C.sub.1
-C.sub.4, more preferably methyl or ##STR9## wherein R.sup.a is
C.sub.1 -C.sub.4 alkyl or R.sup.10 and R.sup.11 together are
alkylene having 3 to 6 carbon atoms, most preferably R.sup.11 is
hydrogen or methyl;
R.sup.12 is chlorine, bromine, iodine, fluorine or C.sub.1 -C.sub.4
alkoxy, preferably methoxy; most preferably R.sup.12 is chlorine,
bromine or methoxy;
R.sup.13 and R.sup.14 independently are (1) hydrogen or an
aliphatic group, preferably hydrogen; (2) halogen, preferably,
fluorine, chlorine or bromine; (3) C.sub.1 -C.sub.4 alkyl,
preferably methyl; (4) C.sub.1 -C.sub.4 aliphatic alkoxy,
preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8)
C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9)
R.sup.b SO.sub.n -- wherein R.sup.b is C.sub.1 -C.sub.4 alkyl,
preferably methyl, C.sub.1 -C.sub.4 haloalkyl, phenyl, benzyl,
--NR.sup.d R.sup.e wherein R.sup.d and R.sup.e independently are
hydrogen or C.sub.1 -C.sub.4 alkyl; and n is the integer 0, 1 or 2,
preferably 2; ##STR10## wherein R.sup.c is C.sub.1 -C.sub.4 alkyl
and R.sup.j is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably
methyl; (11) R.sup.f C(O) wherein R.sup.f is hydrogen, C.sub.1
-C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4
alkoxy; (12) --NR.sup.g R.sup.h wherein R.sup.g and R.sup.h
independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (13) C.sub.1
-C.sub.4 alkylthio or less preferably (14) R.sup.13 and R.sup.14
together can form a ring structure with two adjacent carbon atoms
of the phenyl ring to which they are attached or less preferably
(15) R.sup.13 and R.sup.14 are the groups phenoxy or substituted
phenoxy wherein the substituent is halogen or halomethyl or
both;
R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are independently the
same or different and are selected from the group consisting of
hydrogen, C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 -C.sub.4
alkyl, more preferably methyl, most preferably hydrogen or methyl,
and their salts;
provided, however, that R.sup.15 and R.sup.16 together may form a
substituted or unsubstituted alkylene ring of 2-5 carbon atoms, the
preferred substituent being 1 or 2 methyl groups.
More preferably, R.sup.13 is chlorine, hydrogen, methyl, alkylthio
or methoxy. Preferably R.sup.14 is hydrogen, chlorine, nitro,
trifluoromethyl, or R.sup.b SO.sub.n wherein R.sup.b is C.sub.1
-C.sub.4 alkyl, preferably methyl and n is the integer 0, 1 or 2,
preferably 2.
The compounds of Embodiment B of this invention can have the
following four structural formulae because of tautomerism:
##STR11## wherein R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are as defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by any base to
give a salt having an anion of the following four resonance forms:
##STR12## wherein R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14,
R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are as defined above.
Examples of cations of these bases are inorganic cations such as
alkali metals e.g. lithium, sodium, and potassium, alkaline earth
metals, e.g. barium, magnesium, calcium and strontium, or organic
cations such as substituted ammonium, sulfonium or phosphonium
wherein the substitutent is an aliphatic or aromatic group.
The term "aliphatic group" is used form Embodiments A and B herein
in a broad sense to cover a large class of organic groups
characterized by being derived from (1) an acylic (open-chain
structure) of the paraffin, olefin and acetylene hydrocarbon series
and their derivatives or (2) alicyclic compounds. The aliphatic
group can have from 1 to 10 carbon atoms.
The term "aromatic group" is used for Embodiments A and B herein in
a broad sense to distinguish from the aliphatic group and includes
a group derived from (1) compounds having 6 to 20 carbon atoms and
characterized by the presence of at least one benzene ring,
including monocyclic, bicyclic and polycyclic hydrocarbons and
their derivatives and (2) heterocyclic compounds having 5 to 19
carbon atoms which are similar in structure and are characterized
by having an unsaturated ring structure containing at least one
atom other than carbon such as nitrogen, sulfur and oxygen and
derivatives of these heterocyclic compounds.
In the above description of the compounds of this invention alkyl
and alkoxy include both straight and branched configurations; for
example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
isobutyl, and tert-butyl.
Embodiment C of this invention relates to certain novel
2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides. The
compounds of of this embodiment have the following structural
formula ##STR13## wherein R.sup.21 is hydrogen or C.sub.1 -C.sub.4
alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl,
most preferably R.sup.21 is hydrogen or methyl;
R.sup.22 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl or ##STR14## wherein R.sup.a
is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.22 is hydrogen or
methyl; or R.sup.21 and R.sup.22 together are alkylene having 3 to
6 carbon atoms;
R.sup.23 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.23 is
hydrogen or methyl;
R.sup.24 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.24 is
hydrogen or methyl;
R.sup.25 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.25 is
hydrogen or methyl;
R.sup.26 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl, most preferably R.sup.26 is
hydrogen;
R.sup.27 and R.sup.28 independently are (1) hydrogen; (2) halogen,
preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4
alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably
methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1
-C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b
SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2;
and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano,
preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently
are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein
R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined, with the proviso that R.sup.27 is not attached to the
6-position.
Preferably, R.sup.27 is in the 3-position. Most preferably R.sup.27
is hydrogen and R.sup.28 is hydrogen, chlorine, bromine, fluorine,
trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1
-C.sub.4 alkyl, preferably methyl.
Salts of the above-described compounds (as defined hereinafter) are
also the subject of the instant invention.
The compounds of this embodiment can have the following four
structural formulae because of tautomerism: ##STR15## wherein
R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26,
R.sup.27 and R.sup.28 are as defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by any base to
give a salt having an anion of the following four resonance forms:
##STR16## wherein R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25,
R.sup.26, R.sup.27 and R.sup.28 are as defined above.
Examples of cations of these bases are inorgaic cations such as
alkali metals e.g. lithium, sodium, and potassium organic cations
such as substituted ammonium, sulfonium or phosphonium wherein the
substitutent is an aliphatic or aromatic group.
Embodiment D of this invention relates to
2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as
herbicides.
The compounds have a nitro substitution in the 2-position of the
phenyl moiety of their compounds. The nitro substitution imparts
exceptional herbicidal activity to the compounds of this
invention.
Embodiment D' of this invention is an herbicidal composition
comprising an herbicidally active
2-(2-nitrobenzoyl)-1,3-cyclohexanedione and an inert carrier
therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione
moiety can be substituted, preferably with the groups hereinafter
recited. More preferably, the 1,3-cyclohexanedione moiety has no
substitution or the 4- or 6-positions are substituted with one or
two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety
can be substituted, preferably with the groups hereinafter
recited.
The novel compounds of Embodiment D have the following structural
formula ##STR17## wherein R.sup.31 is hydrogen or C.sub.1 -C.sub.4
alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl,
most preferably R.sup.31 is hydrogen or methyl;
R.sup.32 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl or ##STR18## wherein R.sup.a
is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.32 is hydrogen or
methyl;
R.sup.31 and R.sup.32 together are alkylene having 3 to 6 carbon
atoms;
R.sup.33 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.33 is
hydrogen or methyl;
R.sup.34 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.34 is
hydrogen or methyl;
R.sup.35 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.35 is
hydrogen or methyl;
R.sup.36 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl, most preferably R.sup.36 is
hydrogen;
R.sup.37 and R.sup.38 independently are (1) hydrogen; (2) halogen,
preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4
alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably
methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1
-C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b
SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2;
and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano,
preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently
are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein
R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined, with the proviso that R.sup.37 is not attached to the
6-position.
Preferably, R.sup.37 is in the 3-position. Most preferably R.sup.37
is hydrogen or C.sub.1 -C.sub.4 alkoxy and R.sup.38 is hydrogen,
chlorine, bromine, fluorine, trifluoromethyl, or R.sup.b SO.sub.2
wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term
"halogen" includes chlorine, bromine, iodine and fluorine. The
terms "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and
t-butoxy. The term "haloalkyl" includes the eight alkyl groups with
one or more hydrogens replaced by chlorine, bromine, iodine or
fluorine.
Salts of the above-described compounds (as defined hereinafter) are
also the subject of the instant invention.
The compounds of this invention can have the following four
structural formulae because of tautomerism: ##STR19## wherein
R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36,
R.sup.37 and R.sup.38 are as defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by any base to
give a salt having an anion of the following four resonance forms:
##STR20## wherein R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35,
R.sup.36, R.sup.37 and R.sup.38 are as defined above.
Examples of cations of these bases are inorganic cations such as
alkali metals e.g. lithium, sodium, and potassium or organic
cations such as substituted ammonium, sulfonium or phosphonium
wherein the substitutent is an aliphatic or aromatic group.
Embodiment E of this invention relates to
2-(2-benzoyl)-1,3-cyclohexanediones and their use as
herbicides.
Embodiment E' of this invention is an herbicidal composition
comprising an herbicidally active 2-(2-C.sub.1 -C.sub.4 alkylthio,
C.sub.1 -C.sub.4 alkylsulfinyl or C.sub.1 -C.sub.4 alkylsulfonyl
benzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The
4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be
substituted, preferably with the groups hereinafter recited. More
preferably, the 1,3-cyclohexanedione moiety has no substitution or
the 4- or 6-positions are substituted with one or two methyl
groups. The 3-, 4- and 5-positions of the benzoyl moiety can be
substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment E have the structural formula
##STR21## wherein n is the interger 0, 1 or 2, preferably 2;
R.sup.40 is C.sub.1 -C.sub.4 alkyl, preferably methyl;
R.sup.41 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl, most preferably R.sup.41 is
hydrogen or methyl;
R.sup.42 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl or ##STR22## wherein R.sup.a
is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.42 is hydrogen or
methyl; or
R.sup.41 and R.sup.42 together are alkylene having 3 to 6 carbon
atoms;
R.sup.43 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.43 is
hydrogen or methyl;
R.sup.44 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.44 is
hydrogen or methyl;
R.sup.45 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.45 is
hydrogen or methyl;
R.sup.46 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl, most preferably R.sup.46 is
hydrogen;
R.sup.47 and R.sup.48 independently are (1) hydrogen; (2) halogen,
preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4
alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably
methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1
-C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b
SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2;
and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano,
preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently
are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein
R.sup.e is C.sub.1 -C.sub.4 alkoxy; or (12) --SO.sub.2 NR.sup.c
R.sup.d wherein R.sup.c and R.sup.d are as defined, with the
proviso that R.sup.47 is not attached to the 6-position.
Preferably, R.sup.47 is in the 3-position. Most preferably R.sup.47
is hydrogen or 3-chlorine and R.sup.48 is hydrogen, chlorine,
bromine, fluorine, trifluoromethyl, or R.sup.b SO.sub.2 wherein
R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl.
The term "C.sub.1 -C.sub.4 " alkyl includes methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The
term "halogen" includes chlorine, bromine, iodine and fluorine. The
term "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term
"haloalkyl" includes the eight alkyl groups with one or more
hydrogens replaced by chloro, bromo, iodo or fluoro.
Salts of the above-described compounds (as defined hereinafter) are
also the subject of the instant invention.
The compounds of this invention can have the following four
structural formulae because of tautomerism: ##STR23## wherein n,
R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45,
R.sup.46, R.sup.47 and R.sup.48 are as defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by any base to
give a salt having an anion of the following four resonance forms:
##STR24## wherein n, R.sup.40, R.sup.41, R.sup.42, R.sup.43,
R.sup.44, R.sup.45, R.sup.46, R.sup.47 and R.sup.48 are as defined
above.
Examples of cations of these bases are inorganic cations such as
alkali metals e.g. lithium, sodium, and potassium, organic cations
such as substituted ammonium, sulfonium or phosphonium wherein the
substituent is an aliphatic or aromatic group.
Embodiment F of this invention relates to
2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as
herbicides.
Embodiment F' of this invention is an herbicidal composition
comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione
and an inert carrier therefor wherein the 2-position of the benzoyl
moiety is substituted with C.sub.1 -C.sub.4 alkyl, preferably
C.sub.1 -C.sub.2 alkyl, optionally substituted with halogen, more
preferably methyl or trifluoromethyl and the 4-position preferably
is substituted with an electron withdrawing group, such as halogen,
cyano, trifluoromethyl or nitro. The 4-, 5- and 6-positions of the
1,3-cyclohexanedione moiety can be substituted, preferably with the
groups hereinafter recited. More preferably, the
1,3-cyclohexanedione moiety has no substitution or the 4- or
6-positions are substituted with one or two methyl groups. The 3-,
4- and 5-positions of the benzoyl moiety can be substituted,
preferably with the groups hereinafter recited.
The novel compounds of Embodiment F have the following structural
formula ##STR25## wherein R.sup.50 is C.sub.1 -C.sub.4 alkyl,
preferably C.sub.1 -C.sub.2 alkyl, optionally substituted with
halogen, more preferably methyl and trifluoromethyl;
R.sup.51 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl, most preferably R.sup.51 is
hydrogen or methyl;
R.sup.52 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl or ##STR26## wherein R.sup.a
is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.52 is hydrogen or
methyl; or
R.sup.51 and R.sup.52 together are alkylene having 3 to 6 carbon
atoms;
R.sup.53 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.53 is
hydrogen or methyl;
R.sup.54 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.54 is
hydrogen or methyl;
R.sup.55 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl; most preferably R.sup.55 is
hydrogen or methyl;
R.sup.56 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1
-C.sub.2 alkyl, more preferably methyl, most preferably R.sup.56 is
hydrogen;
R.sup.57 and R.sup.58 independently are (1) hydrogen; (2) halogen,
preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4
alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably
methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1
-C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b
SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2;
and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano,
preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently
are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein
R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or
(12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined, with the proviso that R.sup.57 is not attached to the
6-position.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term
"halogen" includes chlorine, bromine, iodine and fluorine. The term
"C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term
"haloalkyl" includes the eight alkyl groups with one or more
hydrogens replaced by chloro, bromo, iodo or fluoro.
Preferably, R.sup.57 is in the 3-position. Most preferably R.sup.57
is hydrogen and R.sup.58 is hydrogen, chlorine, bromine, fluorine,
trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1
-C.sub.4 alkyl, preferably methyl.
Salts of the above-described compounds (as defined hereinafter) are
also the subject of the instant invention.
The compounds of this invention can have the following four
structural formulae because of tautomerism: ##STR27## wherein
R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55,
R.sup.56, R.sup.57 and R.sup.58 are as defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by any base to
give a salt having an anion of the following four resonance forms:
##STR28## wherein R.sup.50, R.sup.51, R.sup.52, R.sup.53 R.sup.54,
R.sup.55, R.sup.56, R.sup.57 and R.sup.58 are as defined above.
Examples of cations of these bases are inorganic cations such as
alkali metals e.g. lithium, sodium, and potassium organic cations
such as substituted ammonium, sulfonium or phosphonium wherein the
substituent is an aliphatic or aromatic group.
Embodiment G of this invention relates to
2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.
Embodiment G' of this invention is an herbicidal composition
comprising an herbicidally active
2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier
therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione
moiety are preferably substituted with groups hereinafter defined,
most preferably with all methyl groups. The benzoyl moiety can be
substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment G have the following structural
formula ##STR29## wherein R.sup.60 is hydrogen; halogen; C.sub.1
-C.sub.2 alkyl, preferably methyl; C.sub.1 -C.sub.2 alkoxy,
preferably methoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl,
preferably trifluoromethyl; R.sup.a SO.sub.n -- wherein n is 0 or
2, preferably 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl, preferably
methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or
difluoromethoxy. Preferably, R.sup.60 is chlorine, bromine, C.sub.1
-C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano,
nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2
alkylsulfonyl; more preferably chlorine, nitro, methyl,
trifluoromethyl or methylsulfonyl; and
R.sup.61 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably
methyl;
R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl;
or
R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene;
R.sup.63 is C.sub.1 -C.sub.4 alkyl, preferably methyl;
R.sup.64 is C.sub.1 -C.sub.4 alkyl, preferably methyl; or
R.sup.63 and R.sup.64 together are C.sub.2 -C.sub.5 alkylene;
R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen,
preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4
alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably
methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1
-C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b
SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2;
and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano,
preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently
are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein
R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; (12)
--SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as
defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c and
R.sup.d are as defined.
Preferably R.sup.65 is in the 3-position. More preferably R.sup.65
is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C.sub.1
-C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl. Most preferably,
R.sup.65 is hydrogen. Preferably R.sup.66 is in the 4-position.
Most preferably R.sup.66 is halogen, cyano, trifluoromethyl, or
R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl,
preferably methyl or C.sub.1 -C.sub.4 haloalkyl, preferably
chloromethyl, difluoromethyl or trifluoromethyl.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term
"halogen" includes chlorine, bromine, iodine and fluorine. The
terms "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and
t-butoxy. The term "C.sub.1 -C.sub.4 haloalkyl" includes the alkyl
groups defined above under C.sub.1 -C.sub.4 alkyl in which one or
more hydrogens is replaced by chlorine, bromine, iodine or
fluorine.
Salts of the above-described compounds (as defined hereinafter) are
included within the scope of the instant invention.
The compounds of this invention can have the following four
structural formulae because of tautomerism: ##STR30## wherein
R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 and
R.sup.66 are as defined above.
The circled proton on each of the four tautomers is reasonably
labile. These protons are acidic and can be removed by reaction
with a base to form a salt having an anion of the following four
resonance forms: ##STR31## wherein R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64, R.sup.65 and R.sup.66 are as defined above.
Examples of cations of these bases are inorganic cations such as
alkalimetals, e.g., lithium, sodium and potassium; the alkaline
earth metals, e.g. calcium and magnesium or ammonium or organic
cations such as substituted ammonium, sulfonium, sulfoxonium or
phosphonium wherein the substituents are aliphatic or aromatic
groups.
Those skilled in the art will recognize in considering the salts of
this invention that varying degrees os association between the
anion and cation will exist depending upon the nature of the
cation. In some instances with a suitable cation, such as copper,
the salt can exist in a chelated form.
The compounds of this invention and their salts are active
herbicides of a general type. That is, they are herbicidally
effective against a wide range of plant species. The method of
controlling undesirable vegetation of the present invention
comprises applying an herbicidally effective amount of the
above-described compounds to the area where control is desired.
The compounds of Embodiments A and A' of the present invention can
be prepared by the following general method. ##STR32##
Generally, mole amounts of the dione and substituted benzoyl
cyanide are used, along with a slight mole excess of zinc chloride.
The two reactants and the zinc chloride are combined in a solvent
such as methylene chloride. A slight mole excess of triethylamine
is slowly added to the reaction mixture with cooling. The mixture
is stirred at room temperature for 5 hours.
The reaction product is worked up by conventional techniques.
The above-described substituted benzoyl cyanide can be prepared
according to the teaching of T. S. Oakwood and C. A. Weisgerber,
Organic Synthesis Collected, Vol. III, pp. 122 (1955).
The following example teaches the synthesis of a representative
compound of Embodiments A and A' of this invention.
EXAMPLE 1-A,A'
2- (2,4-Dichlorobenzoyl)-cyclohexane-1,3-dione ##STR33##
1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole)
2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous,
powdered zinc chloride were combined in 100 milliliters (ml)
methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly
added with cooling. The reaction mixture was stirred at room
temperature for 5 hours and then poured into 2N hydrochloric acid.
The aqueous phase was discarded and the organic phase was washed
with 150 ml 5% Na.sub.2 CO.sub.3 four times. The aqueous washings
were combined and acidified with HCl, extracted with methylene
chloride, dried and concentrated to yield 25.3 g of crude product.
The crude product was dissolved in ether and stirred with 250 ml of
5% copper (II) acetate. The resulting copper salt was filtered,
washed with ether and stirred with 6N hydrochloric acid to destroy
the salt. The extract was washed with ether to yield 22.15 grams of
the desired product m.p. 138.degree.-140.degree. C. (77.7% yield).
The structure was confirmed by instrumental analysis.
The compounds of Embodiment B of the present invention can be
prepared by the following general method. ##STR34##
Generally, mole amounts of the dione and substituted benzoyl
cyanide are used, along with a slight mole excess of zinc chloride.
The two reactants and the zinc chloride are combined in a solvent
such as methylene chloride. A slight mole excess of triethylamine
is slowly added to the reaction mixture with cooling. The mixture
is stirred at room temperature for 5 hours.
The reaction product is worked up by conventional techniques.
The above-described substituted benzoyl cyanide can be prepared
according to the teaching of T. S. Oakwood and C. A. Weisgerber,
Organic Synthesis Collected, Vol. III, pp. 122 (1955).
The following example teaches the synthesis of a representative
compound of Embodiment B of this invention.
EXAMPLE 1-B
4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione
##STR35##
4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0
g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole)
anhydrous, powdered zinc chloride were combined in 100 milliliters
(ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was
slowly added with cooling. The reaction mixture was stirred at room
temperature for 5 hours and then poured into 2N hydrochloric acid.
The aqueous phase was discarded and the organic phase was washed
with 150 ml 5% Na.sub.2 CO.sub.3 four times. The aqueous washings
were combined and acidified with HCl, extracted with methylene
chloride, dried and concentrated to yield 25.3 g of crude product.
The crude product was chromatographed (2% AcOH/CH.sub.2 Cl.sub.2)
in 5 g aliquots then reduced on rotavap under reduced pressure at
50.degree. C. for 30 minutes to remove AcOH. This yielded an oil
(40% yield). The structure was confirmed by instrumental
analysis.
The compounds of Embodiment C of the present invention can be
prepared by the following general method. ##STR36##
Generally, in step (1) mole amounts of the dione and substituted
benzoyl chloride are used, along with a slight mole excess of
triethylamine. The two reactants are combined in a solvent such as
methylene chloride. The triethylamine is slowly added to the
reaction mixture with cooling. The mixture is stirred at room
temperature for several hours.
The reaction product is worked up by conventional techniques.
##STR37##
Generally, in step (2) a mole of the enol ester intermediate is
reacted with 1 to 4 moles of the triethylamine, preferably 2 moles
of the triethylamine and up to 0.5 mole, preferably 0.1 mole of a
cyanide source (e.g., potassium cyanide or acetone cyanohydrin).
The mixture is stirred in a reaction pot for about one hour at room
temperature and the desired product is recovered by conventional
techniques.
The above described substituted benzoyl chlorides can be prepared
from the corresponding substituted benzoic acids according to the
teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser
and M. Fieser, pp. 767-769 (1967). ##STR38## wherein R.sup.27 and
R.sup.28 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of
general methods according to the teaching of the The Chemistry of
Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons,
New York, N.Y. (1969) and Survey of Organic Synthesis, C. A.
Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are two representative examples of the methods
described therein. ##STR39## wherein R.sup.27 and R.sup.28 are as
previously defined.
In reaction (a) the substituted acetophenone is heated to reflux
for several hours in an aqueous hypochlorite solution. The mixture
is cooled and the reaction product is isolated by conventional
techniques. ##STR40## wherein R.sup.27 and R.sup.28 are as
previously defined.
In reaction (b) the substituted toluene is heated to reflux in an
aqueous solution of potassium permanganate for several hours. The
solution is then filtered and the reaction product is isolated by
conventional techniques.
The following example teaches the synthesis of a representative
compound of Embodiment C of this invention.
EXAMPLE 1-C
2-(2'-Cyanobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR41##
2-Cyanobenzoyl chloride (3.9 g, 24 mmol) and
4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 24 mmol) were dissolved
in 75 ml methylene chloride. Triethylamine (5.0 ml, 36 mmol) was
added dropwise and the resulting solution stirred for one and
one-half hours at room temperature. The solution was washed with
water, 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate
solution (5% K.sub.2 CO.sub.3) and saturated sodium chloride
solution (brine), dried over anhydrous magnesium sulfate
(MgSO.sub.4) and concentrated under vacuum. The residue was
dissolved in 20 ml acetonitrile. Triethylamine (4.4 ml, 32 mmol)
and acetone cyanohydrin (5 drops) were added and the solution
stirred for two hours. After dilution with ether, the solution was
washed with 2N HCl and extracted with 5% K.sub.2 CO.sub.3. The
aqueous extract was acidified with concentrated hydrochloric acid
and extracted with ether. The ether was washed with water and
brine, dried (MgSO.sub.4) and concentrated under vacuum. The
residue was purified by silica gel chromatography, yielding 1.2 g
of a viscous oil which was identified as the desired compound by
nuclear magnetic resonance spectroscopy, infrared spectroscopy and
mass spectroscopy.
The compounds of Embodiments D and D' of the present invention can
be prepared by the following two-step general method.
The process proceeds via the production of an enol ester
intermediate as shown in reaction (1). The final product is
obtained by rearrangement of the enol ester as shown in reaction
(2). The two reactions may be conducted as separate steps by
isolation and recovery of the enol ester using conventional
techniques prior to conducting step (2), or by addition of a
cyanide source to the reaction medium after the formation of the
ester, or in one step by inclusion of the cyanide source at the
start of reaction (1). ##STR42## wherein R.sup.31 through R.sup.38
and moderate base are as defined and X is halogen, preferably
chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1 -C.sub.4
alkoxy-C(O)-O- or ##STR43## wherein R.sup.37 and R.sup.38 in this
portion of the molecule are identical with those in the reactant
shown above and the moderate base is as defined, preferably
tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate or alkali
metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted
benzoyl reactant are used, along with a mole amount or excess of
the base. The two reactants are combined in an organic solvent such
as methylene chloride, toluene, ethyl acetate or dimethylformamide.
The base or benzoyl reactant preferably are added to the reaction
mixture with cooling. The mixture is stirred at 0.degree.
C.-50.degree. C. until the reaction is substantially complete.
##STR44## wherein the moderate base and R.sup.31 through R.sup.38
are as defined above.
Generally, in step (2) a mole of the enol ester intermediate is
reacted with 1 to 4 moles of the base, preferably about 2 moles of
moderate base and from 0.01 mole to about 0.5 mole or higher,
preferably around 0.1 mole of the cyanide source (e.g., potassium
cyanide or acetone cyanohydrin). The mixture is stirred in a
reaction pot until the rearrangement is substantially complete at a
temperature below 50.degree. C., preferably about 20.degree. C. to
about 40.degree. C., and the desired product is recovered by
conventional techniques.
The term "cyanide source" refers to a substance or substances which
under the rearrangement conditions consists of or generates
hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a
source of cyanide anion and/or hydrogen cyanide, together with a
molar excess, with respect to the enol ester, of a moderate
base.
Preferred cyanide sources are alkali metal cyanides such as sodium
and potassium cyanide; cyanohydrins of methyl alkyl ketones having
from 1-4 carbon atoms in the alkyl groups, such as acetone or
methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde
or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde,
propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl)
silyl cyanides, notably trimethyl silyl cyanide; and hydrogen
cyanide itself. Hydrogen cyanide is considered most advantageous as
it produces relatively rapid reaction and is inexpensive. Among
cyanohydrins the preferred cyanide source is acetone
cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent
based on the enol ester. It may be used in as little as about 1
mole percent to produce an acceptable rate of reaction at about
40.degree. C. on a small scale. Larger scale reactions give more
reproducible results with slightly higher catalyst levels of about
2 mole percent. Generally about 1-10 mole % of the cyanide source
is preferred.
The process is conducted with a molar excess, with respect to the
enol ester, of a moderate base. By the term "moderate base" is
meant a substance which acts as a base yet whose strength or
activity as a base lies between that of strong bases such as
hydroxides (which could cause hydrolysis of the enol ester) and
that of weak bases such as bicarbonates (which would not function
effectively). Moderate bases suitable for use in this embodiment
include both organic bases such as tertiary amines and inorganic
bases such as alkali metal carbonates and phosphates. Suitable
tertiary amines include trialkylamines such as triethylamine.
Suitable inorganic bases include potassium carbonate and trisodium
phosphate.
The base is used in an amount of from about 1 to about 4 moles per
mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly
potassium cyanide, a phase transfer catalyst may be included in the
reaction. Particularly suitable phase transfer catalysts are the
Crown ethers.
A number of different solvents may be usable in this process,
depending on the nature of the acid chloride or the acylated
product. A preferred solvent for this reaction is
1,2-dichloroethane. Other solvents which may be employed, depending
on the reactants or products include toluene, acetonitrile,
methylene chloride, ethyl acetate, dimethylformamide, and methyl
isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the
cyanide source, the rearrangement may be conducted at temperatures
up to about 50.degree. C.
The above described substituted benzoyl chlorides can be prepared
from the corresponding substituted benzoic acids according to the
teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser
and M. Fieser, pp. 767-769 (1967). ##STR45## wherein R.sup.37 and
R.sup.38 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of
general methods according to the teaching of The Chemistry of
Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons,
New York, N.Y. (1969) and Survey of Organic Synthesis, C. A.
Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods
described therein. ##STR46## wherein R.sup.37 and R.sup.38 are as
previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in
aqueous sulfuric acid for several hours. The mixture is cooled and
the reaction product is isolated by conventional techniques.
##STR47## wherein R.sup.37 and R.sup.38 are as previously
defined.
In reaction (b) the substituted acetophenone is heated to reflux
for several hours in an aqueous hypochlorite solution. The mixture
is cooled and the reaction product is isolated by conventional
techniques. ##STR48## wherein R.sup.37 and R.sup.38 are as
previously defined.
In reaction (c) the substituted toluene is heated to reflux in an
aqueous solution of potassium permanganate for several hours. The
solution is then filtered and the reaction product is isolated by
conventional techniques.
The following examples teach the synthesis of representative
compounds of Embodiment D and D' of this invention.
EXAMPLE 1-D,D'
2-(2'-Nitrobenzoyl)-1,3-cyclohexanedione ##STR49##
2-Nitrobenzoyl chloride (5.0 g, 27 mmol) and cyclohexanedione (3.0
g, 27 mmol) were dissolved in methylene chloride. Triethylamine
(4.9 ml, 35 mmol) was added dropwise and the resulting solution
stirred for one hour. The solution was washed with 2 normal
hydrochloric acid (2N HCl), water, 5% potassium carbonate solution
and saturated sodium chloride solution, dried over anhydrous
magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The
residue was dissolved in 20 ml acetonitrile. Triethylamine (1
equivalent) and potassium cyanide (40 mol %) were added and the
solution stirred for one hour at room temperature. After dilution
with ether, the solution was washed with 2N HCl and extracted with
5% potassium carbonate solution. The aqueous extract was acidified
and ether was added. Filtration of the resulting mixture yielded
3.2 g of the desired compound (m.p. 132.degree.-135.degree. C.)
which was identified by nuclear magnetic resonance spectroscopy,
infrared spectroscopy and mass spectroscopy.
EXAMPLE 2-D,D'
2-(2'-Nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione ##STR50##
Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylene
chloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and
5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for
one hour at room temperature an additional 3 equivalents of
triethylamine and 0.4 ml acetone cyanohydrin were added. The
solution was stirred for 2.5 hours, then washed with 2N HCl and
extracted with 5% potassium carbonate solution. The basic extracts
were acidified with 2N HCl and extracted with ether. The ether
portion was washed with saturated sodium chloride solution, dried
over anhydrous magnesium sulfate and concentrated under vacuum. The
residue was recrytallized from ethyl acetate yielding 2.0 g of the
desired compound (m.p. 130.degree.-133.degree. C.) which was
identified as such by nuclear magnetic resonance spectroscopy,
infrared spectroscopy and mass spectroscopy.
The compounds of Embodiments E and E' of the present invention can
be prepared by the following two or three step general method.
The process proceeds via the production of an enol ester
intermediate as shown in reaction (1). The final product is
obtained by rearrangement of the enol ester as shown in reaction
(2). The two reactions may be conducted as separate steps by
isolation and recovery of the enol ester using conventional
techniques prior to conducting step (2), or by addition of a
cyanide source to the reaction medium after the formation of the
enol ester, or in one step by inclusion of the cyanide source at
the start of reaction (1). ##STR51## wherein moderate base, and
R.sup.40 through R.sup.48 are defined herein, and X is halogen,
preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1
-C.sub.4 alkoxy-C(O)-O- or ##STR52## wherein R.sup.40, R.sup.47 and
R.sup.48 in this portion of the moledule are identical with those
in the reactant shown above, and the moderate base is as defined,
preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate
or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted
benzoyl reactant are used, along with a mole amount or excess of
the base. The two reactants are combined in an organic solvent such
as methylene chloride, toluene, ethyl acetate or dimethylformamide.
The base or benzoyl reactant preferably are added to the reaction
mixture with cooling. The mixture is stirred at 0.degree.
C.-50.degree. C. until the reaction is substantially complete.
##STR53##
Generally, in step (2) a mole of the enol ester intermediate is
reacted with 1 to 4 moles of the base, preferably about 2 moles of
moderate base and from 0.01 mole to about 0.5 mole or higher,
preferably around 0.1 mole of the cyanide source (e.g., potassium
cyanide or acetonecyanohydrin). The mixture is stirred in a
reaction pot until the rearrangement is substantially complete at a
temperature below 50.degree. C., preferably about 20.degree. C. to
about 40.degree. C., and the desired product is recovered by
conventional techniques.
The term "cyanide source" refers to a substance or substances which
under the rearrangement conditions consists of or generates
hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a
source of cyanide anion and/or hydrogen cyanide, together with a
molar excess, with respect to the enol ester, of a moderate
base.
Preferred cyanide sources are alkali metal cyanides such as sodium
and potassium cyanide; cyanohydrins of methyl alkyl ketones having
from 1-4 carbon atoms in the alkyl groups, such as acetone or
methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde
or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde,
propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl)
silyl cyanides, notably trimethyl silyl cyanide; and hydrogen
cyanide itself. Hydrogen cyanide is considered most advantageous as
it produces relatively rapid reaction and is inexpensive. Among
cyanohydrins the preferred cyanide source is acetone
cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent
based on the enol ester. It may be used in as little as about 1
mole percent to produce an acceptable rate of reaction at about
40.degree. C. on a small scale. Larger scale reactions give more
reproducible results with slightly higher catalyst levels of about
2 mole percent. Generally about 1-10 mole % of the cyanide source
is preferred.
The process is conducted with a molar excess, with respect to the
enol ester, of a moderate base. By the term "moderate base" is
meant a substance which acts as a base yet whose strength or
activity as a base lies between that of strong bases such as
hydroxides (which could cause hydrolysis of the enol ester) and
that of weak bases such as bicarbonates (which would not function
effectively). Moderate bases suitable for use in this embodiment
include both organic bases such as tertiary amines and inorganic
bases such as alkali metal carbonates and phosphates. Suitable
tertiary amines include trialkylamines such as triethylamine.
Suitable inorganic bases include potassium carbonate and trisodium
phosphate.
The base is used in an amount of from about 1 to about 4 moles per
mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly
potassium cyanide, a phase transfer catalyst may be included in the
reaction. Particularly suitable phase transfer catalysts are the
Crown ethers.
A number of different solvents may be usable in this process,
depending on the nature of the acid chloride or the acylated
product. A preferred solvent for this reaction is 1,
2-dichloroethane. Other solvents which may be employed, depending
on the reactants or products include toluene, acetonitrile,
methylene chloride, ethyl acetate, dimethylformamide, and methyl
isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the
cyanide source, the rearrangment may be conducted at temperatures
up to about 50.degree. C. ##STR54## wherein n is 1 or 2.
Generally in step (3), a mole of the reaction product of step (2)
is reacted with a slight mole or two mole excess of of an oxidizing
agent such as m-chloroperbenzoic acid after being dissolved in a
solvent such as methylene chloride. After completion of the
reaction, the resulting mixture is stripped under vacuum. The
residue is purified by silica gel chromatography to yield the
desired product.
The above described substituted benzoyl chlorides can be prepared
from the corresponding substituted benzoic acids according to the
teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser
and M. Fieser, pp. 767-769 (1967). ##STR55## wherein R.sup.40,
R.sup.47 and R.sup.48 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of
general methods according to the teaching of the The Chemistry of
Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons
New York, N.Y. (1969) and Survey of Organic Synthesis, C. A.
Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods
described therein. ##STR56## wherein R.sup.40, R.sup.47 and
R.sup.48 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in
aqueous sulfuric acid for several hours. The mixture is cooled and
the reaction product is isolated by conventional techniques.
##STR57## wherein R.sup.40, R.sup.47 and R.sup.48 are as previously
defined.
In reaction (b) the substituted acetophenone is heated to reflux
for several hours in an aqueous hypochlorite solution. The mixture
is cooled and the reaction product is isolated by conventional
techniques. ##STR58## wherein R.sup.40, R.sup.47 and R.sup.48 are
as defined and X is chlorine, bromine or iodine.
In reaction (c) the substituted aromatic halide is allowed to react
with magnesium in a solvent such as ether. The solution is then
poured over crushed dry ice and the benzoic acid is isolated by
conventional techniques.
The following examples teach the synthesis representative compounds
of Embodiments E and E' of this invention.
EXAMPLE 1-E,E'
2-(2'-Methylthiobenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione
##STR59##
2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and
4,4,6-trimethylcyclohexanedione (5.0 g, 39 mmol) were dissolved in
methylene chloride. Triethylamine (7.0 ml, 50 mmol) was added
dropwise and the resulting solution stirred for one hour at room
temperature. The solution was washed with 2 normal hydrochloric
acid (2N HCl), 5% potassium carbonate solution (5% K.sub.2
CO.sub.3) and saturated sodium chloride solution (brine), dried
over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated
under vacuum. The residue was dissolved in 20 ml acetonitrile.
Triethylamine (2.5 equivalents) and acetone cyanohydrin (0.4 ml)
were added and the solution stirred for 45 minutes at room
temperature. After dilution with ether, the solution was washed
with 2N HCl and extracted with 5% K.sub.2 CO.sub.3. The aqueous
extract was acidified with hydrochloric acid and extracted with
ether. The ether was washed with brine, dried (MgSO.sub.4) and
concentrated under vacuum. The residue was purified by trituration
with ether, yielding 5.0 g of a viscous oil which was identified as
the desired compound by nuclear magnetic resonance spectroscopy
(nmr), infrared spectroscopy (ir) and mass spectroscopy (ms).
EXAMPLE 2-E,E'
2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl -1,3-cyclohexanedione
##STR60##
The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9
mmol) was dissolved in 40 ml methylene chloride. m-Chloroperbenzoic
acid (3.5 g, 16 mmol) was added and the resulting solution was
stirred for 45 minutes. The solution was concentrated under vacuum.
Purification of the residue by silica gel chromatography yielded
1.7 g of a viscous oil which was identified as the desired compound
by nmr, ir and ms.
EXAMPLE 3-E,E'
2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl-1,3-cyclohexa
nedione ##STR61##
2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3-cyclohexanedio
ne (5.0 g, 14 mmol) (which was prepared according to the method of
Example 1) was dissolved in 50 ml methylene chloride. A solution of
m-chloroperbenzoic acid (2.4 g--80%, 14 mmol) in 50 ml methylene
chloride was added dropwise and the resulting solution was stirred
for three hours at room temperature. After concentration under
vacuum, the residue was dissolved in ether and washed with 1%
hydrochloric acid. A 5% copper (II) acetate solution was added to
the ether fraction, followed by hexane. The liquid phase was
decanted and the remaining gummy solid stirred with 6N HCl and
ether. The ether layer was dried (MgSO.sub.4) and concentrated to
give 4.7 of a thick yellow solid. Purification on a centrifugally
accelerated thin layer chromatograph (4 mm silica gel, 50:50:1
hexane:ethyl acetate:acetic acid-eluent) yielded 2.4 g of a viscous
oil which was identified as the desired compound by nmr, ir and
ms.
The compounds of Embodiments F and F' of the present invention can
be prepared by the following two-step general method.
The process proceeds via the production of an enol ester
intermediate as shown in reaction (1). The final product is
obtained by rearrangement of the enol ester as shown in reaction
(2). The two reactions may be conducted as separate steps by
isolation and recovery of the enol ester using conventional
techniques prior to conducting step (2), or by addition of a
cyanide source to the reaction medium after the formation of the
enol ester, or in one step by inclusion of the cyanide source at
the start of reaction (1). ##STR62## wherein R.sup.50 through
R.sup.58 are as defined and X is halogen, preferably chlorine,
C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1 -C.sub.4 alkoxy-C(O)-O- or
##STR63## wherein R.sup.50, R.sup.57 and R.sup.58 in this portion
of the molecule are identical with those in the reactant shown
above and the moderate base is as defined, preferably tri-C.sub.1
-C.sub.6 alkylamine, alkali metal carbonate or alkali metal
phosphate.
Generally, in step (1) mole amounts of the dione and substituted
benzoyl reactant are used, along with a mole amount or excess of
the base. The two reactants are combined in an organic solvent such
as methylene chloride, toluene, ethyl acetate or dimethylformamide.
The base or benzoyl reactant preferably are added to the reaction
mixture with cooling. The mixture is stirred at 0.degree.
C.-50.degree. C. until the reaction is substantially complete.
The reaction product is worked up by conventional techniques.
##STR64## wherein R.sup.50 through R.sup.58 are as defined.
Generally, in step (2) a mole of the enol ester intermediate is
reacted with 1 to 4 moles of the base, preferably about 2 moles of
moderate base and from 0.01 mole to about 0.5 mole or higher,
preferably around 0.1 mole of the cyanide source (e.g., potassium
cyanide or acetone cyanohydrin). The mixture is stirred in a
reaction pot until the rearrangement is substantially complete at a
temperature below 80.degree. C., preferably about 20.degree. C. to
about 40.degree. C., and the desired product is recovered by
conventional techniques.
The term "cyanide source" refers to a substance or substances which
under the rearrangement conditions consists of or generates
hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a
source of cyanide anion and/or hydrogen cyanide, together with a
molar excess, with respect to the enol ester, of a moderate
base.
Preferred cyanide sources are alkali metal cyanides such as sodium
and potassium cyanide; cyanohydrins of methyl alkyl ketones having
from 1-4 carbon atoms in the alkyl groups, such as acetone or
methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde
or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde,
propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl)
silyl cyanides, notably trimethyl silyl cyanide; and hydrogen
cyanide itself. Hydrogen cyanide is considered most advantageous as
it produces relatively rapid reaction and is inexpensive. Among
cyanohydrins the preferred cyanide source is acetone
cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent
based on the enol ester. It may be used in as little as about 1
mole percent to produce an acceptable rate of reaction at about
40.degree. C. on a small scale. Larger scale reactions give more
reproducible results with slightly higher catalyst levels of about
2 mole percent. Generally about 1-10 mole % of the cyanide source
is preferred.
The process is conducted with a molar excess, with respect to the
enol ester, of a moderate base. By the term "moderate base" is
meant a substance which acts as a base yet whose strength or
activity as a base lies between that of strong bases such as
hydroxides (which could cause hydrolysis of the enol ester) and
that of weak bases such as bicarbonates (which would not function
effectively). Moderate bases suitable for use in this embodiment
include both organic bases such as tertiary amines and inorganic
bases such as alkali metal carbonates and phosphates. Suitable
tertiary amines include trialkylamines such as triethylamine.
Suitable inorganic bases include potassium carbonate and trisodium
phosphate.
The base is used in an amount of from about 1 to about 4 moles per
mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly
potassium cyanide, a phase transfer catalyst may be included in the
reaction. Particularly suitable phase transfer catalysts are the
Crown ethers.
A number of different solvents may be usable in this process,
depending on the nature of the acid chloride or the acylated
product. A preferred solvent for this reaction is
1,2-dichloroethane. Other solvents which may be employed, depending
on the reactants or products include toluene, acetonitrile,
methylene chloride, ethyl acetate, dimethylformamide, and methyl
isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the
cyanide source, the rearrangment may be conducted at temperatures
up to about 50.degree. C.
The above described substituted benzoyl chlorides can be prepared
from the corresponding substituted benzoic acids according to the
teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser
and M. Fieser, pp. 767-769 (1967). ##STR65## wherein R.sup.50,
R.sup.57 and R.sup.58 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of
general methods according to the teaching of The Chemistry of
Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons,
New York, N.Y. (1969) and Survey of Organic Synthesis, C. A.
Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are four representative examples of the methods
described therein. ##STR66## wherein R.sup.50, R.sup.57 and
R.sup.58 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in
aqueous sulfuric acid for several hours. The mixture is cooled and
the reaction product is isolated by conventional techniques.
##STR67## wherein R.sup.50, R.sup.57 and R.sup.58 are as previously
defined.
In reaction (b) the substituted acetophenone is heated to reflux
for several hours in an aqueous hypochlorite solution. The mixture
is cooled and the reaction product is isolated by conventional
techniques. ##STR68## wherein R.sup.50, R.sup.57 and R.sup.58 are
as defined and X is chlorine, bromine or iodine.
The substituted aromatic halide is allowed to react with magnesium
in a solvent such as ether. The solution is then poured over
crushed dry ice and the benzoic acid is isolated by conventional
techniques.
The following example teachs the synthesis of a representative
compound of Embodiments F and F' of this invention.
EXAMPLE 1-F,F'
2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione
##STR69##
4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mmol) and
4,4,6-trimethyl-1,3-cyclohexanedione (2.3 g, 15 mmol) were
dissolved in 100 ml methylene chloride. The solution was cooled
with an ice bath and triethylamine (2.1 ml, 15 mmol) in 10 ml
methylene chloride was added dropwise. The ice bath was then
removed and the resulting solution stirred for 30 minutes at room
temperature. The solution was washed with 2N hydrochloric acid (2N
HCl), 5% potassium carbonate solution (5% K.sub.2 CO.sub.3) and
saturated sodium chloride solution (brine), dried over anhydrous
magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The
residue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine
(3.5 ml, 25 mmol) and 0.4 ml acetone cyanohydrin were added and the
solution stirred for two hours at room temperature while protected
by a drying tube (calcium sulfate). After dilution with ether, the
solution was washed with 2N HCl and extracted with 5 % K.sub.2
CO.sub.3. The aqueous extract was acidified with concentrated
hydrochloric acid and extracted with ether. The ether was washed
with brine, dried (MgSO.sub.4) and concentrated under vacuum. The
resulting oil was purified on a silica gel column (80:20:1
hexane:ethyl acetate: acetic acid-eluent), yielding 1.5 g of a
viscous oil which was identified as the desired compound by nuclear
magnetic resonance spectroscopy, infrared spectroscopy and mass
spectroscopy.
The compounds of Embodiment G and G' of the present invention can
be prepared by the following two-step general method.
The process proceeds via the production of an enol ester
intermediate as shown in reaction (1). The final product is
obtained by rearrangement of the enol ester as shown in reaction
(2). The two reactions may be conducted as separate steps by
isolation and recovery of the enol ester using conventional
techniques prior to conducting step (2), or by addition of a
cyanide source to the reaction medium after the formation of the
enol ester, or in one step by inclusion of the cyanide source at
the start of reaction (1). ##STR70## wherein R.sup.60 through
R.sup.66 and moderate base are as defined and X is halogen,
preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1
-C.sub.4 alkoxy-C(O)-O- or ##STR71## wherein R.sup.60, R.sup.65 and
R.sup.66 in this portion of the molecule are identical with those
in the reactant shown above and the moderate base is as defined,
preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate
or alkali metal phosphate.
Generally, in step (1) mole amounts of the trione and substituted
benzoyl reactant are used, along with a mole amount or excess of
the base. The two reactants are combined in an organic solvent such
as methylene chloride, toluene, ethyl acetate or dimethylformamide.
The base or benzoyl reactant preferably is added to the reaction
mixture with cooling. The mixture is stirred at 0.degree.
C.-50.degree. C. until the reaction is substantially complete.
##STR72## wherein the moderate base and R.sup.60 through R.sup.66
are as defined above.
Generally, in step (2) a mole of the enol ester intermediate is
reacted with 1 to 4 moles of the moderate base, preferably about 2
moles of moderate base and from 0.01 mole to about 0.5 mole or
higher, preferably about 0.1 mole of the cyanide source (e.g.,
potassium cyanide or acetone cyanohydrin). The mixture is stirred
in a reaction pot until the rearrangement is substantially complete
at a temperature below 50.degree. C., preferably about 20.degree.
C. to about 40.degree. C., and the desired product is recovered by
conventional techniques.
The term "cyanide source" refers to a substance or substances which
under the rearrangement conditions consists of or generates
hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a
source of cyanide anion and/or hydrogen cyanide, together with a
molar excess, with respect to the enol ester, of a moderate
base.
Preferred cyanide sources are alkali metal cyanides such as sodium
and potassium cyanide; cyanohydrins of methyl alkyl ketones having
from 1-4 carbon atoms in the alkyl groups, such as acetone or
methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde
or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde,
propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl)
silyl cyanides, notably trimethyl silyl cyanide; and hydrogen
cyanide itself. Hydrogen cyanide is considered most advantageous as
it produces relatively rapid reaction and is inexpensive. Among
cyanohydrins the preferred cyanide source is acetone
cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent
based on the enol ester. It may be used in as little as about 1
mole percent to produce an acceptable rate of reaction at about
40.degree. C. on a small scale. Larger scale reactions give more
reporducible results with slightly higher catalyst levels of about
2 mole percent. Generally about 1-10 mole % of the cyanide source
is preferred.
The process is conducted with a molar excess, with respect to the
enol ester, of a moderate base. By the term "moderate base" is
meant a substance which acts as a base yet whose strength or
activity as a base lies between that of strong bases such as
hydroxides (which could cause hydrolysis of the enol ester) and
that of weak bases such as bicarbonates (which would not function
effectively). Moderate bases suitable for use in this embodiment
include both organic bases, e.g., trialkylamines such as
triethylamine and inorganic bases such as alkali metal carbonates
and phosphates. Suitable inorganic bases include potassium
carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per
mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly
potassium cyanide, a phase transfer catalyst may be included in the
reaction. Particularly suitable phase transfer catalysts are the
crown ethers.
A number of different solvents are useful in this process,
depending on the nature of the acid halide or the acylated product.
A preferred solvent for this reaction is 1,2-dichloroethane. Other
solvents which may be employed, depending on the reactants or
products include toluene, acetonitrile, methylene chloride, ethyl
acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the
cyanide source, the rearrangment may be conducted at temperatures
up to about 50.degree. C.
The above described substituted benzoyl chlorides can be prepared
from the corresponding substituted benzoic acids according to the
teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser
and M. Fieser, pp. 767-769 (1967). ##STR73## wherein R.sup.60,
R.sup.65 and R.sup.66 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of
general methods according to the teaching of The Chemistry of
Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons,
New York, N. Y. (1969) and Survey of Organic Synthesis, C. A.
Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods
described therein. ##STR74## wherein R.sup.60, R.sup.65 and
R.sup.66 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in
aqueous sulfuric acid for several hours. The mixture is cooled and
the reaction product is isolated by conventional techniques.
##STR75## wherein R.sup.60, R.sup.65 and R.sup.66 are as previously
defined.
In reaction (b) the substituted acetophenone is heated to reflux
for several hours in an aqueous hypochlorite solution. The mixture
is cooled and the reaction product is isolated by conventional
techniques. ##STR76## wherein R.sup.60, R.sup.65 and R.sup.66 are
as previously defined.
In reaction (c) the substituted toluene is heated to reflux in an
aqueous solution of potassium permanganate for several hours. The
solution is then filtered and the reaction product is isolated by
conventional techniques.
The following example teaches the synthesis of a representative
compound of Embodiment G and G' of this invention.
EXAMPLE 1-G,G'
2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione
##STR77##
2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and
4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were
dissolved in methylene chloride. Triethylamine was added and the
resulting solution stirred at room temperature for 30 minutes. The
solution was washed with 1 normal hydrochloric acid (1N HCl), and
saturated sodium chloride (brine), dried over anhydrous magnesium
sulfate (MgSO.sub.4) and concentrated under vacuum. The residue was
dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5
equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were
added and the mixture stirred at room temperature for 4 hours.
After dilution with ether, the solution was washed with 1N HCl and
extracted with 5% K.sub.2 CO.sub.3. The basic extract was acidified
with HCl and extracted with ether. The ether extract was washed
with brine, dried over MgSO.sub.4 and concentrated under vacuum,
yielding 2.2 g of crude product. This was recrystallized from
benzene to remove syncarpic acid still present. Concentration of
the mother liquor under vacuum gave 1.7 g of the desired product as
an oil, which solidified on standing (m.p. 76.degree.-82.degree.
C.). It was identified as such by nuclear magnetic resonance
spectroscopy, infrared spectroscopy and mass spectroscopy.
The following are tables of certain selected compounds of
Embodiments A-G' that are preparable according to the procedures
described herein. Compound numbers are assigned to each compound
and are used throughout the remainder of the application.
TABLE I-A
__________________________________________________________________________
##STR78## Cmpd. n.sub.D.sup.30 or No. R R.sup.1 R.sup.2 R.sup.3
R.sup.4 R.sup.5 m.p. .degree.C.
__________________________________________________________________________
1A CH.sub.3 CH.sub.3 Cl H H H 1.5613 2A CH.sub.3 CH.sub.3 Cl H 4-Cl
H 1.5655 3A CH.sub.3 CH.sub.3 Cl H H 6-Cl 103-108 4A* H H Cl H 4-Cl
H 138-140 5A CH.sub.3 CH.sub.3 Br H H H 6A CH.sub.3 CH.sub.3 Cl H H
5-Cl 74-77 7A H H Cl H H 5-Cl 104-107 8A H H Br H H H 93-96 9A H H
Cl H H H 79-87 10A H H I H H H 66-70 11A H H Cl H 4-NO.sub.2 H
118-122 12A H H Cl H H 6-Cl 143-148 13A H H Cl H H 5-Br 109-115 14A
H H I 3-I H 5-I 164-167 15A H H Cl H H 5-CH.sub.3 60-65 16A H H Cl
H 4-CH.sub.3 H 79-86 17A H H Cl H 4-CH.sub.3 O H 60-63 18A H H Cl
3-Cl H 6-Cl 19A H H Cl H H 5-CH.sub.3 O 77-80 20A H H Cl 3-Cl H H
80-90 21A H H Cl H H 5-CF.sub.3 74-75 22A H H Cl H H 5-NO.sub.2
140-143 23A H H Cl 3-Cl 4-Cl H 152-154 24A H H Cl 3-Cl 4-CH.sub.3 O
H 169-170 25A H H Cl H 4-Br H 104-107 26A CH.sub.3 CH.sub.3
CH.sub.3 O H H H 104-108 27A H H Cl H ##STR79## H 28A H H Br H H
(a) 29A H H CH.sub.3 O 3-CH.sub.3 O H H 75-79 30A H H CH.sub.3 O H
H 5-CH.sub.3 O 89-92 31A H H Br H 4-CH.sub.3 O 5-CH.sub.3 O 92-96
32A H H Br H (4)-OCH.sub.2 O-(5) 63-68 33A CH.sub.3 CH.sub.3 Cl
3-Cl 4-Cl H 86-89 34A H H Cl 3-Cl H 5-Cl 35A CH.sub.3 CH.sub.3 Cl
3-Cl H 5-Cl 105-109 36A CH.sub.3 CH.sub.3 Cl 3-Cl 4-Cl 5-Cl 137-139
37A H H Cl 3-Cl 4-Cl 5-Cl 106-110 38A H H Cl H 4-Cl 5-Cl 108-111
39A ##STR80## H Cl H 4-Cl H 40A ##STR81## H Cl H 4-Cl H 41A
CH(CH.sub.3).sub.2 H Cl H 4-Cl H 42A CH(CH.sub.3).sub.2 H Cl 3-Cl
4-Cl H 43A H H Cl H 4-F H 44A sodium salt of Compound No. 23 85-94
45A isopropylamine salt of Compound No. 23 160-165 46A
triethylamine salt of Compound No. 23 82-85 47A potassium salt of
Compound No. 23 107-106 48A triethanolammonium salt of Compound No.
39 49A sodium salt of Compound No. 43 60-63 50A CH(CH.sub.3).sub.2
H Cl 3-CH.sub.3 O 4-Br H 51A H H Cl H 4-CH.sub.3 SO.sub.2 H 140-141
52A H CH.sub.3 Cl H 4-Cl H 53A i-C.sub.4 H.sub.9 H Cl H 4-Cl H 54A
i-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 O H H 55A CH.sub.3 CH.sub.3 Cl H
4-CH.sub.3 SO.sub.2 H 56A CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-Cl H
57A H H Cl 3-CH.sub.3 4-Cl H 56-64 58A H H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 H 98-102 59A H H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H
98-109 60A H H Cl H 4-C.sub.3 H.sub.7 SO.sub.2 H semi-solid 61A H H
Cl 3-CH.sub.3 O 4-CH.sub.3 SO.sub.2 H 48-59 62A CH.sub.3 CH.sub.3
Cl H 4-n-C.sub.3 H.sub.7 SO.sub.2 H semi-solid 63A H H Cl 3-Cl
4-n-C.sub.3 H.sub.7 SO.sub.2 H 145-148.5 64A H H Cl 3-C.sub.2
H.sub.5 S 4-C.sub.2 H.sub.5 SO.sub.2 H oil 65A CH.sub.3 CH.sub.3 Cl
H 4-C.sub.2 H.sub.5 SO.sub.2 H 103-108 66A CH.sub.3 CH.sub.3 Cl
3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H 108-114 67A i-C.sub.3 H.sub.7 H
Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H brown gum 68A H H Cl 3-Cl
4-CH.sub.3 SO.sub.2 H 145-154 69A i-C.sub.3 H.sub.7 H Cl 3-Cl
4-CH.sub.3 SO.sub.2 H 70A H H Br H 4-CH.sub.3 SO.sub.2 H brown gum
71A H H Cl H 4-i-C.sub.3 H.sub.7 SO.sub.2 H semi-solid 72A H H Cl H
4-CH.sub.3 S H 74-77 73A H H Cl 3-Cl 4-CH.sub.3 S H 74A CH.sub.3
CH.sub.3 Cl 3-Cl 4-n-C.sub.3 H.sub.7 SO.sub.2 H 120-123 75A H H Cl
H 4-n-C.sub.4 H.sub.9 SO.sub.2 H semi-solid 76A CH.sub.3 CH.sub.3
Cl H 4-n-C.sub.4 H.sub.9 SO.sub.2 H 77A H H Cl 3-C.sub.2 H.sub.5 O
4-CH.sub.3 SO.sub.2 H semi-solid 78A H H Cl 3-CH.sub.3 O
4-n-C.sub.3 H.sub.7 SO.sub.2 H golden gum 79A CH.sub.3 CH.sub.3 Cl
H 4-i-C.sub.3 H.sub.7 SO.sub.2 H 125-128 80A CH(CH.sub.3).sub.2 H
CH.sub.3 O 3-Cl 5-Cl H 81A H H Cl 3-CH.sub.3 O 4-Br H 110-111 82A H
H Cl 3-CH.sub.3 4-Cl H 56-64 83A H H Cl H 4-Cl 5-CH.sub.3 O softens
>70 84A CH(CH.sub.3).sub.2 H Cl 3-n-C.sub.3 H.sub.7 O 4-Br H 85A
H H Cl 3-C.sub.2 H.sub.5 O 4-Br H 101-104 86A H H Cl H 4-i-C.sub.4
H.sub.9 SO.sub.2 H 136-140 87A CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.4
H.sub.9 SO.sub.2 H 88A H H Cl 3-Cl 4-i-C.sub.3 H.sub.7 SO.sub.2 H
173-176 89A H H Cl 3-Cl 4-n-C.sub.4 H.sub.9 SO.sub.2 H 135-138 90A
H H Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2 H.sub.5 SO.sub.2 H gum 91A H H
Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 SO.sub.2 H gum 92A H H Cl 3-Cl
4-C.sub.2 H.sub.5 S H 91-94 93A H H Cl 3-C.sub.2 H.sub.5 S
4-n-C.sub.3 H.sub.7 SO.sub.2 H oil 94A H H Cl 3-C.sub.2 H.sub.5 S
4-C.sub.2 H.sub.5 S H oil 95A H H Cl H 4-(CH.sub.3).sub.2 NSO.sub.2
H oil 96A H H Cl 3-C.sub.2 H.sub.5 O 4-n-C.sub.3 H.sub.7 SO.sub.2 H
97A H H Cl 3-n-C.sub.3 H.sub.7 O 4-C.sub.2 H.sub.5 SO.sub.2 H oil
98A CH.sub.3 CH.sub.3 Cl H 4-(CH.sub.3).sub.2 NSO.sub.2 H oil 99A H
H Cl H 4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2 H 90-92 100A CH.sub.3
CH.sub.3 Cl H 4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2 H 101A H H Cl H
4-C.sub.2 H.sub.5 S H 102A H H Cl H 4-n-C.sub.3 H.sub.7 S H 103A H
H Cl H 4-i-C.sub.3 H.sub.7 S H 104A H H Cl H 4-C.sub.2 H.sub.5 SO H
105A H H CH.sub.3 O H 4-NO.sub.2 H semi-solid 106A H H Cl
3-n-C.sub.3 H.sub.7 O 4-Br H 107A H H Cl 3-n-C.sub.3 H.sub.7 O
4-CH.sub.3 SO.sub.2 H 96-100 108A H H Cl 3-allyloxy 4-CH.sub.3
SO.sub.2 H semi-solid 109A H H Cl 3-CH.sub.3 C(O)NH 4-Cl H 155-160
110A H H Cl 3-Cl 4-n-C.sub.3 H.sub.7 S H 111A
H H Cl 3-CH.sub.3 O 4-NO.sub.2 H 150-153 112A H H Cl 3-allyloxy
4-C.sub.2 H.sub.5 SO.sub.2 H 113A H H Cl 3-CH.sub.2 BrCHBrCH.sub.2
O 4-C.sub.2 H.sub.5 SO.sub.2 H 114A H H Cl 3-n-C.sub.4 H.sub.9 O
4-C.sub.2 H.sub.5 SO.sub.2 H gum 115A H H Cl 3-i-C.sub.4 H.sub.9 O
4-C.sub.2 H.sub.5 SO.sub.2 H 116A H H Cl H 4-allylthio H 117A
CH.sub.3 CH.sub.3 Cl H 4-NO.sub.2 H 118A H H Cl 3-CH.sub.3
C(O)N(CH.sub.3) 4-Cl H 119A H H Cl 3-i-C.sub.3 H.sub.7 O 4-C.sub.2
H.sub.5 SO.sub.2 H 120A H H Cl 3-CH.sub.2 ClCH.sub.2 CH.sub.2 O
4-C.sub.2 H.sub.5 SO.sub. H gum 121A H H Cl H 4-t-C.sub.4 H.sub.9 S
H 122A H H Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 S H 123A H H Cl H
4-CF.sub.3 H 124A H H Cl H 4-Cl 6-Cl 125A H H Cl 3-CH.sub.3
C(O)N(CH.sub.3) H H 131-135 126A H H Cl 3-CH.sub.3 C(O)NH H H 127A
H H Cl 3-(CH.sub.3).sub.2 N 4-Cl H 128A CH.sub.3 H Cl 3-CH.sub.3 O
4-CH.sub.3 SO.sub.2 H 117-122 129A H H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 H 130A H H Br H H H 131A H H Br H 4-C.sub.2 H.sub.5 OC(O)
H 132A H H Cl H 4-CN H 183-184 133A H H Cl 3-CH.sub.3 C(O)NH H
6-NO.sub.2 134A H H Cl 3-(CH.sub.3).sub.2 N H H 135A H H Cl 3-Cl
4-ClCH.sub.2 CH.sub.2 SO.sub.2 H
__________________________________________________________________________
*Prepared in Example 1A. ##STR82##
TABLE I-B
__________________________________________________________________________
##STR83## Compound Number R.sup.10 R.sup.11 R.sup.12 R.sup.13
R.sup.14 R.sup.15 R.sup.16 R.sup.17 R.sup.18
__________________________________________________________________________
1B ##STR84## H Cl H 4-Cl H H H H 2B ##STR85## CH.sub.3 Cl H 4-Cl H
H H H 3B triethanolammonium salt of Compound No. 2 4B
triethanolammonium salt of Compound No. 7 5B ##STR86## CH.sub.3 Cl
3-Cl 4-Cl H H H H 6B triethanolammonium salt of Compound No. 5
.sup. CH.sub.3a) CH.sub.3 Cl H 4-Cl H H H H 8B CH.sub.3 CH.sub.3 Cl
H 4-Cl CH.sub.3 H H H 9B CH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-Cl H H H
H 10B CH.sub.3 H Cl H 4-Cl H H H H 11B CH.sub.3 H Cl H 4-Cl
CH.sub.3 H H H 12B C.sub.5 H.sub.10 Cl H 4-Cl H H H H 13B CH.sub.3
CH.sub.3 Cl 3-Cl 4-Cl H H H H 14B CH.sub.3 CH.sub.3 Cl 3-Cl 4-Cl
CH.sub.3 H H H 15B i-C.sub.3 H.sub.7 H Cl 3-Cl 4-Cl H H H H 16B
CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 SO.sub.2 H H H H 17B CH.sub.3
CH.sub.3 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H 18B CH.sub.3 H Cl
H 4-CH.sub.3 SO.sub.2 H H H H 19B CH.sub.3 CH.sub.3 Cl 3-Cl
4-CH.sub.3 SO.sub.2 H H H H 20B CH.sub.3 CH.sub.3 Cl 3-Cl 4-C.sub.2
H.sub.5 SO.sub.2 H H H H 21B CH.sub.3 CH.sub.3 Cl H 4-C.sub.2
H.sub.5 SO.sub.2 H H H H 22B CH.sub.3 CH.sub.3 Cl H 4-C.sub.2
H.sub.5 SO.sub.2 CH.sub.3 H H H 23B CH.sub.3 CH.sub.3 Cl
3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H H 24B CH.sub.3
CH.sub.3 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H 25B CH.sub.3
CH.sub.3 Cl 3-CH.sub.3 4-Cl H H H H 26B CH.sub.3 CH.sub.3 Cl
3-OCH.sub.3 4-Cl H H H H 27B CH.sub.3 C.sub.2 H.sub.5 Cl H 4-Cl H H
H H 28B CH.sub.3 CH.sub.3 Cl H H H H H H 29B CH.sub. 3 CH.sub.3 Cl
3-OCH.sub.3 4-Br H H H H 30B CH.sub.3 CH.sub.3 Cl H 4-Br H H H H
31B CH.sub.3 C.sub.2 H.sub.5 Cl 3-Cl 4-Cl H H H H 32B n-C.sub.3
H.sub.7 H Cl H 4-Cl H H H H 33B ##STR87## n-C.sub.3 H.sub.7 Cl H
4-Cl H H H H 34B CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.3 H.sub.7
SO.sub.2 H H H H 35B CH.sub.3 CH.sub.3 Cl 3-i-C.sub.3 H.sub.7 O
4-Br H H H H 36B CH.sub.3 CH.sub.3 Cl H 6-F H H H H 37B i-C.sub.3
H.sub.7 H Cl 3-Cl 4-Cl H H H H 38B CH.sub.3 CH.sub.3 Cl 3-OC.sub.2
H.sub.5 4-Br CH.sub.3 H H H 39B i-C.sub.3 H.sub.7 OC(O) H Cl H 4-Cl
H H H H 40B C.sub.2 H.sub.5 OC(O) n-C.sub.3 H.sub.7 Cl H 4-Cl H H H
H 41B C.sub.5 H.sub.10 Cl H 4-Cl H H H H 42B CH.sub.3 CH.sub.3 Cl H
4-Cl H H CH.sub.3 H 43B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7
SO.sub.2 H H H H 44B CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.3 H.sub.7
SO.sub.2 H H H H 45B CH.sub.3 CH.sub.3 CH.sub.3 O 3-CH.sub.3 O H H
H H H 46B CH.sub.3 CH.sub.3 CH.sub.3 O H 4-Cl H H H H 47B CH.sub.3
CH.sub.3 Cl H 4-Br CH.sub.3 H H H 48B CH.sub.3 CH.sub.3 Br H H H H
H H 49B CH.sub.3 CH.sub.3 I H H H H H H 50B CH.sub.3 CH.sub.3 F H H
H H H H 51B CH.sub.3 CH.sub.3 CH.sub.3 O H H H H H H 52B CH.sub.3
CH.sub.3 Cl 3-allyloxy 4-Br H H H H 53B CH.sub.3 CH.sub.3 Cl H
4-CH.sub.3 SO.sub.2 H H CH.sub.3 H 54B CH.sub.3 CH.sub.3 Cl
3-CH.sub.3 O 4-Br CH.sub.3 H H H 55B CH.sub.3 CH.sub.3 Br H 4-CN H
H H H 56B CH.sub.3 CH.sub.3 Cl H 4N(CH.sub.3)SO.sub.2 CF.sub.3 H H
H H 57B CH.sub.3 CH.sub.3 Cl 3-NO.sub.2 H H H H H 58B CH.sub.3
CH.sub.3 C.sub.2 H.sub.5 O H 4-Cl H H H H 59B CH.sub.3 CH.sub.3 Cl
H 4-i-C.sub.4 H.sub.9 SO.sub.2 H H H H 60B CH.sub.3 CH.sub.3 Cl
3-C.sub.2 H.sub.5 O 4-CH.sub.3 SO.sub.2 H H H H 61B CH.sub.3
CH.sub.3 Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 SO.sub.2 H H H H 62B
CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.4 H.sub.9 SO.sub.2 H H H H 63B
CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H H
H 64B CH.sub.3 CH.sub.3 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3
H H H 65B CH.sub.3 CH.sub.3 Cl H 4-F H H H H 66B CH.sub.3 H Cl
3-CH.sub.3 O 4-Br H H H H 67B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 O H H
H H H 68B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 S 4-n-C.sub.3
H.sub.7 SO.sub.2 H H H H 69B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5
S 4-C.sub.2 H.sub.5 S H H H H 70B CH.sub.3 CH.sub.3 Cl 3-C.sub.2
H.sub.5 S 4-C.sub.2 H.sub.5 SO.sub.2 H H H H 71B CH.sub.3 CH.sub.3
Cl 3-C.sub.2 H.sub.5 S 4-CH.sub.3 SO.sub.2 H H H H 72B CH.sub.3
CH.sub.3 Cl Cl 4-i-C.sub.3 H.sub.7 SO.sub.2 H H H H 73B CH.sub.3
CH.sub.3 Cl 3-Cl 4-n-C.sub.4 H.sub.9 SO.sub.2 H H H H 74B CH.sub.3
CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2 H.sub.5 SO.sub.2 H H H H
75B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-Br H H H H 76B
CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-n-C.sub.3 H.sub.7
SO.sub.2 H H H H 77B CH.sub.3 CH.sub.3 Cl 3-n-C.sub.3 H.sub.7 O
4-C.sub.2 H.sub.5 SO.sub.2 H H H H 78B CH.sub.3 CH.sub. 3 Cl H
4-(CH.sub.3).sub.2 NSO.sub.2 H H H H 79B CH.sub.3 CH.sub.3 Cl
3-CH.sub.3 S 4-C.sub.2 H.sub.5 SO.sub.2 H H H H 80B CH.sub.3
CH.sub.3 Cl 3-Cl 4-C.sub.2 H.sub.5 S H H H H 81B CH.sub.3 CH.sub.3
Cl H 4-C.sub.2 H.sub.5 S H H H H
82B CH.sub.3 CH.sub.3 Cl H 4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2 H H
H H 83B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO.sub.2 H H H H
84B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 S CH.sub.3 H H H 85B
CH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 S(O) H H H H 86B CH.sub.3
CH.sub.3 Cl H 4-i-C.sub.3 H.sub.7 S H H H H 87B CH.sub.3 CH.sub.3
Cl 3-Cl 4-n-C.sub.3 H.sub.7 S H H H H 88B CH.sub.3 CH.sub.3 Cl H
4-t-C.sub.4 H.sub.9 SO.sub.2 H H H H 89B CH.sub.3 CH.sub.3 Cl H
4-i-C.sub.3 H.sub.7 S CH.sub.3 H H H 90B CH.sub.3 CH.sub.3 Cl H
4-n-C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H H H 91B CH.sub.3 CH.sub.3
Cl * 4-Cl H H H H 92B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.2CHCH.sub.2 S
H H H H 93B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2
H.sub.5 S H H H H 94B CH.sub.3 CH.sub.3 Cl 3-Cl 4-CH.sub.3 S
CH.sub.3 H H H 95B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 S H H H H 96B
CH.sub.3 CH.sub.3 Cl 3-i-C.sub.3 H.sub.7 O 4-C.sub.2 H.sub.5
SO.sub.2 H H H H 97B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 O 4-C.sub.2
H.sub.5 S H H H H 98B CH.sub.3 CH.sub.3 Cl ** 4-Cl H H H H 99B
CH.sub.3 CH.sub.3 Cl ** H H H H H 100B CH.sub.3 CH.sub.3 Cl 3-Cl
4-CH.sub.3 S H H H H 101B CH.sub.3 CH.sub.3 CH.sub.3 O H 4-NO.sub.2
H H H H 102B CH.sub.3 CH.sub.3 CH.sub.3 O H 4-CF.sub. 3 H H H H
103B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO H H H H 104B
CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO CH.sub.3 H H H
__________________________________________________________________________
.sup.a) Prepared in Example IB. *3-CH.sub.3 C(O)NH **3-CH.sub.3
C(O)N(CH.sub.3)
The following additional compounds can be prepared by the general
method hereinbefore taught.
TABLE I-B
__________________________________________________________________________
##STR88## R.sup.10 R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15
R.sup.16 R.sup.17 R.sup.18
__________________________________________________________________________
CH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-Cl CH.sub.3 H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl H 4-Cl H H H H CH.sub.3 n-C.sub.4 H.sub.9 Cl H
4-Cl CH.sub.3 H H H C.sub.2 H.sub.5 H Cl H 4-Cl H H H H C.sub.2
H.sub.5 H Cl H 4-Cl CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl H 4-Cl H
H H H n-C.sub.4 H.sub.9 H Cl H 4-Cl CH.sub.3 H H H i-C.sub. 3
H.sub.7 H Cl H 4-Cl H H H H i-C.sub.3 H.sub.7 H Cl H 4-Cl CH.sub.3
H H H C.sub.5 H.sub.10 Cl H 4-Cl CH.sub.3 H H H CH.sub.3 n-C.sub.3
H.sub.7 Cl 3-Cl 4-Cl H H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl
4-Cl CH.sub.3 H H H CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-Cl H H H H
CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-Cl CH.sub.3 H H H CH.sub.3 H
Cl 3-Cl 4-Cl H H H H CH.sub.3 H Cl 3-Cl 4-Cl CH.sub.3 H H H C.sub.2
H.sub.5 H Cl 3-Cl 4-Cl H H H H C.sub.2 H.sub.5 H Cl 3-Cl 4-Cl
CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl 3-Cl 4-Cl H H H H n-C.sub.4
H.sub.9 H Cl 3-Cl 4-Cl CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-Cl 4-Cl
H H H H C.sub.5 H.sub.10 Cl 3-Cl 4-Cl CH.sub.3 H H H CH.sub.3
n-C.sub.3 H.sub.7 Cl H 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3
n-C.sub.3 H.sub.7 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl H 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3
H Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl H
4-CH.sub.3 SO.sub.2 H H H H C.sub.2 H.sub.5 H Cl H 4-CH.sub.3
SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl H 4-CH.sub.3
SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl H 4-CH.sub.3 SO.sub.2
CH.sub.3 H H H i-C.sub.3 H.sub.7 H Cl H 4-CH.sub.3 SO.sub.2 H H H H
i-C.sub.3 H.sub.7 H Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.
5 H.sub.10 Cl H 4-CH.sub.3 SO.sub.2 H H H H C.sub.5 H.sub.10 Cl H
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl
3-Cl 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.4 H.sub.9 Cl
3-Cl 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 H Cl 3-Cl 4-CH.sub.3
SO.sub.2 H H H H CH.sub.3 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H
H H C.sub.2 H.sub.5 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H H C.sub.2
H.sub.5 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H n-C.sub.4
H.sub.9 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H H n-C.sub.4 H.sub.9 H
Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H i-C.sub.3 H.sub.7 H Cl
3-Cl 4-CH.sub.3 SO.sub.2 H H H H i-C.sub.3 H.sub.7 H Cl 3-Cl
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-Cl
4-CH.sub.3 SO.sub.2 H H H H C.sub.5 H.sub.10 Cl 3-Cl 4-CH.sub.3
SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl
4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl
3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.4
H.sub.9 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H
CH.sub.3 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3 H Cl
3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl
3-Cl 4-C.sub.2 H.sub.5 SO.sub. 2 H H H H C.sub.2 H.sub.5 H Cl 3-Cl
4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl
3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl 3-Cl
4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H i-C.sub.3 H.sub.7 H Cl
3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H H i-C.sub.3 H.sub.7 H Cl 3-Cl
4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-Cl
4-C.sub.2 H.sub.5 SO.sub.2 H H H H C.sub.5 H.sub.10 Cl 3-Cl
4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3
H.sub.7 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3 n-C.sub.3
H.sub.7 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H
CH.sub.3
H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3 H Cl H 4-C.sub.2
H.sub.5 SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl H 4-C.sub.2
H.sub.5 SO.sub.2 H H H H C.sub.2 H.sub.5 H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H i-C.sub.3 H.sub.7 H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 H H H H i-C.sub.3 H.sub.7 H Cl H 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H C.sub.5 H.sub.10 Cl H 4-C.sub.2 H.sub.5
SO.sub.2 H H H H C.sub.5 H.sub.10 Cl H 4-C.sub.2 H.sub.5 SO.sub.2
CH.sub.3 H H H CH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3
4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl
3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H H
CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H CH.sub.3 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 H H H H CH.sub.3 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-C.sub.2
H.sub.5 SO.sub.2 H H H H C.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-C.sub.2
H.sub.5 SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3
4-C.sub.2 H.sub.5 SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl
3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H i-C.sub.3
H.sub.7 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H H
i-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2
CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 H H H H C.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-C.sub.2
H.sub.5 SO.sub.2 H H H H CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-C.sub.2
H.sub.5 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl
3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H H CH.sub.3 n-C.sub.3
H.sub.7 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H
CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2
H H H H CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H CH.sub.3 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 H H H H CH.sub.3 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-C.sub.2
H.sub.5 SO.sub.2 H H H H C.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-C.sub.2
H.sub.5 SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl 3-CH.sub.3
4-C.sub.2 H.sub.5 SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl
3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H i-C.sub.3
H.sub.7 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H H
i-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2
CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 H H H H C.sub.5 H.sub.10 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5
SO.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-CH.sub.3
SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3
4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl
3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.4
H.sub.9 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H
CH.sub.3 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 H Cl
3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl
3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H C.sub.2 H.sub.5 H Cl
3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H
Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl
3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H i-C.sub.3 H.sub.7 H
Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H i-C.sub.3 H.sub.7 H Cl
3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.5 H.sub.10 Cl
3-OCH.sub.3
4-CH.sub.3 SO.sub.2 H H H H C.sub.5 H.sub.10 Cl 3-OCH.sub.3
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 Cl 3-CH.sub.3
4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 CH.sub.3 Cl 3-CH.sub.3
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 n-C.sub.3 H.sub.7
Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 n-C.sub.4
H.sub.9 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H
CH.sub.3 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H H CH.sub.3 H Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.2 H.sub.5 H Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H H C.sub.2 H.sub.5 H Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H n-C.sub.4 H.sub.9 H
Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H H n-C.sub.4 H.sub.9 H Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H i-C.sub.3 H.sub.7 H
Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H H i-C.sub.3 H.sub.7 H Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H C.sub.5 H.sub.10 Cl
3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H C.sub.5 H.sub.10 Cl 3-CH.sub.3
4-CH.sub.3 SO.sub.2 CH.sub.3 H H H CH.sub.3 CH.sub.3 Cl 3-CH.sub.3
4-Cl CH.sub.3 H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-Cl H
H H H CH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H H
CH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-Cl H H H H CH.sub.3
n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H H CH.sub.3 H Cl
3-CH.sub.3 4-Cl H H H H CH.sub.3 H Cl 3-CH.sub.3 4-Cl CH.sub.3 H H
H C.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-Cl H H H H C.sub.2 H.sub.5 H Cl
3-CH.sub.3 4-Cl CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl 3-CH.sub.3
4-Cl H H H H n-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-Cl CH.sub.3 H H H
i-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-Cl H H H H i-C.sub.3 H.sub.7 H
Cl 3-CH.sub.3 4-Cl CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-CH.sub.3
4-Cl H H H H C.sub.5 H.sub.10 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H H
CH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H H CH.sub.3
n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-Cl H H H H CH.sub.3 n-C.sub.3
H.sub.7 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H H CH.sub.3 n-C.sub.4
H.sub.9 Cl 3-OCH.sub.3 4-Cl H H H H CH.sub.3 n-C.sub.4 H.sub.9 Cl
3-OCH.sub.3 4-Cl CH.sub.3 H H H CH.sub.3 H Cl 3-OCH.sub.3 4-Cl H H
H H CH.sub.3 H Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H H C.sub.2 H.sub.5 H
Cl 3-OCH.sub.3 4-Cl H H H H C.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-Cl
CH.sub.3 H H H n-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-Cl H H H H
n-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H H i-C.sub.3
H.sub.7 H Cl 3-OCH.sub.3 4-Cl H H H H i-C.sub.3 H.sub.7 H Cl
3-OCH.sub.3 4-Cl CH.sub.3 H H H C.sub.5 H.sub.10 Cl 3-OCH.sub.3
4-Cl H H H H C.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H H
CH.sub.3 CH.sub.3 Cl 3-n-C.sub.3 H.sub.7 O 4-Br H H H H CH.sub.3
CH.sub.3 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H CH.sub.3
CH.sub.3 Cl H 4-NO.sub.2 H H H H CH.sub.3 CH.sub.3 Cl 3-C.sub.2
H.sub.5 O 4-CH.sub.3 S H H H H CH.sub.3 CH.sub.3 Cl H 4-CN H H H H
CH.sub.3 CH.sub.3 Cl 3-(CH.sub.3).sub.2 N 4-Cl H H H H
__________________________________________________________________________
TABLE I-C
__________________________________________________________________________
##STR89## Comp. No. R.sup.21 R.sup.22 R.sup.23 R.sup.24 R.sup.25
R.sup.26 R.sup.27 R.sup.28 n.sub.D.sup.30 or m.p.
__________________________________________________________________________
.sup. 1C.sup.a CH.sub.3 CH.sub.3 H H H H H H oil 2C H H H H H H H
CN 124-140.degree. C.
__________________________________________________________________________
.sup.a Prepared in Example IC.
TABLE I-D
__________________________________________________________________________
##STR90## Comp. No. R.sup.31 R.sup.32 R.sup.33 R.sup.34 R.sup.35
R.sup.36 R.sup.37 R.sup.38 n.sub.D.sup.30 or
__________________________________________________________________________
m.p. 1D CH.sub.3 H H H H H H H viscous oil 2D CH.sub.3 CH.sub.3 H H
CH.sub.3 H H H viscous oil 3D.sup.a) H H H H H H H H 132-135 4D
CH.sub.3 CH.sub.3 H H H H H H viscous oil 5D.sup.b) H H CH.sub.3
CH.sub.3 H H H H 130-133 6D CH.sub.3 H H H CH.sub.3 H H H viscous
oil 7D CH.sub.3 CH.sub.3 H H H H H CF.sub.3 52-61 8D H H H H H H H
CF.sub.3 88-94 9D H H CH.sub.3 CH.sub.3 H H H CF.sub.3 89-97 10D
CH.sub.3 CH.sub.3 H H H H 3-CH.sub.3 H 119-122 11D CH.sub.3
CH.sub.3 H H H H 3-Cl H 72-79 12D CH.sub.3 CH.sub.3 H H H H H Cl
118-121 13D CH.sub.3 CH.sub.3 H H H H 5-Cl H 118-120 14D CH.sub.3
CH.sub.3 H H H H 5-F H 130-133 15D CH.sub.3 CH.sub.3 H H H H
3-CH.sub.3 O H 139-142 16D CH.sub.3 CH.sub.3 CH.sub.3 H H H H
CF.sub.3 viscous oil 17D CH.sub.3 CH.sub.3 H H H H H NO.sub.2
viscous oil 18D CH.sub.3 CH.sub.3 H H H H H Br viscous oil 19D
CH.sub.3 CH.sub.3 H H H CH.sub.3 5-CH.sub.3 H viscous oil 20D
CH.sub.3 CH.sub.3 H H H H 5-CH.sub.3 H viscous oil 21D H H H H H H
H F 123-128 22D CH.sub.3 CH.sub.3 H H H H H F viscous oil 23D H H H
H H H H Cl viscous oil 24D CH.sub.3 CH.sub.3 H H H H H SO.sub.2
CH.sub.3 130-133 25D CH.sub.3 CH.sub.3 H H H H H SO.sub.2
-n-C.sub.3 H.sub.7 viscous oil 26D H H H H H H H SO.sub.2 CH.sub.3
157-159 27D H H H H H H H SO.sub.2 -n-C.sub.3 H.sub.7 120-123 28D
CH.sub.3 CH.sub.3 H H H H 5-F H 165-195 29D CH.sub.3 CH.sub.3 H H H
H H SO.sub.2C.sub.2 H.sub.5 oil 30D CH.sub.3 CH.sub.3 H H CH.sub.3
H H SO.sub.2CH.sub.3 gum 31D CH.sub.3 n-C.sub.4 H.sub.9 H H H H H H
viscous oil 32D H H i-C.sub.4 H.sub.9 H H H H H viscous oil 33D H H
H H H H H SO.sub.2C.sub.2 H.sub.5 viscous oil 34D H H H H H H H CN
viscous oil 35D H H H H H H H SO.sub.2 N(CH.sub.3).sub.2 158-159
36D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 N(CH.sub.3).sub.2 120-130
37D H H H H H H H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 158-163 38D
CH.sub.3 CH.sub.3 H H H H H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 oil
39D CH.sub.3 CH.sub.3 H H H H H ##STR91## oil 40D H H CH.sub.3
CH.sub.3 H H H SO.sub.2N(C.sub.2 H.sub.5).sub.2 oil 41D H H H H H H
H SC.sub.2 H.sub.5 oil 42D H H H H H H H S(O)-n-C.sub.3 H.sub.7 oil
43D H H H H H H H S-n-C.sub.3 H.sub.7 oil 44D CH.sub.3 CH.sub.3 H H
CH.sub.3 H H S-n-C.sub.3 H.sub.7 oil 45D CH.sub.3 CH.sub.3 H H H H
H S-n-C.sub.3 H.sub.7 oil 46D CH.sub.3 CH.sub.3 H H CH.sub.3 H H
SC.sub.2 H.sub.5 oil 47D CH.sub.3 CH.sub.3 H H H H H SC.sub.2
H.sub.5 oil 48D H H H H H H H SCH.sub.3 94-97 49D CH.sub.3 CH.sub.3
H H CH.sub.3 H H CF.sub.3 oil 50D CH.sub.3 CH.sub.3 H H H H H
SCH.sub.3 oil 51D c) H i-C.sub.3 H.sub.7 H H H H H 145-148 52D
CH.sub.3 CH.sub.3 H H H H 5-CH.sub.3 O Br oil 53D H H CH.sub.3
CH.sub.3 H H H Cl oil 54D H H H H H H 3-CH.sub.3 O Cl oil 55D
CH.sub.3 CH.sub.3 H H H H 3-CH.sub.3 O Cl oil 56D CH.sub.3 CH.sub.3
H H CH.sub.3 H H CH.sub.3 S oil 57D H H H H H H H ##STR92## 120-125
58D H H CH.sub.3 CH.sub.3 H H H CN 175-177 59D CH.sub.3 CH.sub.3 H
H H H H CN 151-153 60D CH.sub.3 CH.sub.3 H H CH.sub.3 H H CN oil
61D c) H H H H H H H oil 62D d) H H H H H H H oil 63D H H CH.sub.3
H H H H Cl 110-115 64D H H CH.sub.3 H H H H SO.sub.2 -n-C.sub.3
H.sub.7 oil 65D d) CH.sub.3 H H H H H Cl oil 66D H H H H H H H
SO.sub.2 CHCl.sub.2 oil 67D CH.sub.3 CH.sub.3 H H H H H SO.sub.2
CHCl.sub.2 oil 68D H H H H H H c) Br oil 69D H H H H H H H SO.sub.2
CH.sub.2 Cl oil 70D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 CH.sub.2
Cl wax 71D d) CH.sub.3 H H H H H H oil 72D H H H H H H C.sub.2
H.sub.5 O Cl oil 73D CH.sub.3 CH.sub.3 H H CH.sub.3 H CH.sub.3 O
CF.sub.3 oil
__________________________________________________________________________
.sup.a) Prepared in Example 1D,D'. .sup.b) Prepared in Example
2D,D'. c) = C.sub. 2 H.sub.5 OC(O)- d) = iC.sub.3 H.sub.7
OC(O)-
TABLE I-E
__________________________________________________________________________
##STR93## Comp. No. n R.sup.40 R.sup.41 R.sup.42 R.sup.43 R.sup.44
R.sup.45 R.sup.46 R.sup.47 R.sup.48 m.p.
__________________________________________________________________________
1E 0 CH.sub.3 H H H H H H H H 79-81.degree. C. 2E 0 CH.sub.3
CH.sub.3 CH.sub.3 H H H H H H oil .sup. 3E.sup.a) 0 CH.sub.3
CH.sub.3 CH.sub.3 H H CH.sub.3 H H H oil .sup. 4E.sup.b) 2 CH.sub.3
CH.sub.3 CH.sub.3 H H CH.sub.3 H H H oil 5E 0 C.sub.2 H.sub.5
CH.sub.3 CH.sub.3 H H H H H H oil 6E 2 C.sub.2 H.sub.5 CH.sub.3
CH.sub.3 H H H H H H oil 7E 0 CH.sub.3 H H H H H H 3-Cl Cl
59-64.degree. C. 8E 2 CH.sub.3 H H H H H H 3-Cl Cl 116-119.degree.
C. 9E 0 CH.sub.3 H H H H H H H CF.sub.3 102-106.degree. C. 10E 2
CH.sub.3 H H H H H H H CF.sub.3 oil 11E 0 CH.sub.3 CH.sub.3
CH.sub.3 H H H H H CF.sub.3 49-53.degree. C. 12E 2 CH.sub.3
CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil 13E.sup.c) 1 CH.sub.3
CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil 14E 0 CH.sub.3 H H H H H H
3-Cl SCH.sub.3 105-107.degree. C. 15E 1 CH.sub.3 H H H H H H 3-Cl
S(O)CH.sub.3 oil 16E 0 CH.sub.3 H H H H H H H SO.sub.2 n-C.sub.3
H.sub.7 oil 17E 0 CH.sub.3 H H H H H H H SCH.sub.3 101-103.degree.
C. 18E 2 CH.sub.3 H H H H H H H SO.sub.2 n-C.sub.3 H.sub.7 oil 19E
2 CH.sub.3 H H H H H H H SO.sub.2 CH.sub.3 194-196.degree. C. 20E 0
CH.sub.3 H H H H H H 3-CH.sub.3 H 40-42.degree. C. 21E 2 CH.sub.3 H
H H H H H 3-CH.sub.3 H 80-86.degree. C.
__________________________________________________________________________
.sup.a) Prepared in Example 1E,E'. .sup.b) Prepared in Example
2E,E'. .sup.c) Prepared in Example 3E,E'.
TABLE I-F
__________________________________________________________________________
##STR94## Comp. n.sub.D.sup.30 No. R.sup.50 R.sup.51 R.sup.52
R.sup.53 R.sup.54 R.sup.55 R.sup.56 R.sup.57 R.sup.58 or m.p.
__________________________________________________________________________
1F CH.sub.3 H H H H H H H H 35-42.degree. C. 2F CH.sub.3 CH.sub.3
CH.sub.3 H H H H H H 47-53.degree. C. 3F CH.sub.3 CH.sub.3 CH.sub.3
H H H H H Br oil 4F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CN oil 5F
CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-NO.sub.2 H oil 6F CH.sub.3
CH.sub.3 CH.sub.3 H H H H 5-Cl H oil 7F CH.sub.3 CH.sub.3 CH.sub.3
H H H H H CH.sub.3 SO.sub.2 oil 8F CH.sub.3 CH.sub.3 CH.sub.3 H H
CH.sub.3 H H CH.sub.3 SO.sub.2 oil 9F CH.sub.3 CH.sub.3 CH.sub.3 H
H H H 3-Cl H oil 10F CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H
C.sub.2 H.sub.5 SO.sub.2 oil 11F CH.sub.3 CH.sub.3 CH.sub.3 H H H H
H C.sub.2 H.sub.5 SO.sub.2 oil 12F CH.sub.3 CH.sub.3 CH.sub.3 H H H
H H n-C.sub.3 H.sub.7 SO.sub.2 oil 13F CH.sub.3 H H H H H H H
CH.sub.3 SO.sub.2 oil 14F CH.sub.3 H H H H H H H n-C.sub.3 H.sub.7
SO.sub.2 oil 15F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CH.sub.3 S
oil 16F C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H H H H H Br oil 17F
CH.sub.3 H H H H H H H CN oil 18F CH.sub.3 CH.sub.3 CH.sub.3 H H H
H H F oil 19F CH.sub.3 H H H H H H H C.sub.2 H.sub.5SO.sub.2 oil
20F CH.sub.3 H H H H H H 3-Cl H 65-67.degree. C. 21F CH.sub.3 H H H
H H H 3-I H oil 22F CH.sub.3 H H H H H H 3-NO.sub.2 H oil 23F
CH.sub.3 H H H H H H 3-CN H 96-101.degree. C. 24F CF.sub.3 CH.sub.3
CH.sub.3 H H H H H H oil 25F CF.sub.3 H H H H H H H H oil 26F
CF.sub.3 CH.sub.3 CH.sub.3 H H H H H Br oil 27F CF.sub.3 H H H H H
H H Cl 82-88.degree. C. 28F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H Cl
oil 29F CF.sub.3 H H H H H H H C.sub.2 H.sub.5 S oil 30F CF.sub.3
CH.sub.3 CH.sub.3 H H H H H C.sub.2 H.sub.5 SO.sub.2 oil 31F
CF.sub.3 H H H H H H H CN oil 32F CF.sub.3 CH.sub.3 CH.sub.3 H H H
H H CN oil 33F.sup.a) CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H
Br oil 34F CH.sub.3 H H H H H H H CH.sub.3 35F CH.sub.3 CH.sub.3
CH.sub.3 H H H H 3-Cl C.sub.2 H.sub.5 SO.sub.2 115-117.degree. C.
36F CH.sub.3 H H H H H H 3-Cl C.sub.2 H.sub.5 SO.sub.2 oil 37F
CH.sub.3 b) b) H H H H 3-CF.sub.3 H oil 38F CH.sub.3 c) H i-C.sub.3
H.sub.7 H H H 3-NO.sub.2 H 88-108.degree. C. 39F CF.sub.3 CH.sub.3
CH.sub.3 H H CH.sub.3 H H CH.sub.3 S oil 40F CF.sub.3 CH.sub.3
CH.sub.3 H H H H H CH.sub.3 S oil 41F CF.sub.3 CH.sub.3 CH.sub.3 H
H CH.sub.3 H H CH.sub.3 SO.sub.2 oil 42F CH.sub.3 CH.sub.3 CH.sub.3
H H H H H CF.sub.3 oil 43F CH.sub.3 H H H H H H H CF.sub.3
114-120.degree. C. 44F CH.sub.3 H H H H H H 3-Cl Cl oil 45F
CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-Cl Cl oil 46F CH.sub.3
CH.sub.3 CH.sub.3 H H H H 3-CF.sub.3 H oil 47F CF.sub.3 H H H H H H
H CH.sub.3 S oil 48F CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H
CF.sub.3 oil 49F CF.sub.3 H H H H H H H CF.sub.3 oil 50F CF.sub.3
CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil 51F CH.sub.3 H H CH.sub.3
H H H H CH.sub.3 SO.sub.2 oil 52F CF.sub.3 CH.sub.3 CH.sub.3 H H
CH.sub.3 H H C.sub.2 H.sub.5 SO.sub.2 oil 53F CH.sub.3 H H H H H H
H Br 94-98.degree. C. 54F CH.sub.3 H H H H H H d) H oil
__________________________________________________________________________
.sup.a) Prepared in Example 1F,F'. b) (CH.sub.2).sub.5 c) C.sub.2
H.sub.5 OC(O)- d) 3N(CH.sub.3)COCH.sub.3
TABLE I-G
__________________________________________________________________________
##STR95## Comp. No. R.sup.60 R.sup.61 R.sup.62 R.sup.63 R.sup.64
R.sup.65 R.sup.66 m.p. .degree.C.
__________________________________________________________________________
1G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H 112-117 .sup.
2G.sup.a) NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl 76-82
3G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3
.sup. 176-179.degree. 4G CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
CH.sub.3 H 4-SO.sub.2 C.sub.2 H.sub.5 gum 5G CF.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 viscous oil 6G NO.sub.2
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.2 Cl oil 7G
Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-F gum 8G Cl CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.2 H.sub.5 4-SO.sub.2 C.sub.2
H.sub.5 gum 9G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H
4-SO.sub.2 CH.sub.3 gum 10G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
H 4-SCH.sub.3 gum 11G CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3
3-NO.sub.2 H gum 12G I CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H gum
13G OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum 14G Cl
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OCH.sub.3 4-Br gum 15G
NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 nC.sub.3
H.sub.7 gum 16G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H
4-SO.sub.2 N(CH.sub.3).sub.2 gum 17G NO.sub.2 CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 H 4-CN .sup. 148-150.degree. 18G SO.sub.2
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H gum 19G NO.sub.2
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 gum 20G H CH.sub.3
CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum 21G H CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 H 4-SCF.sub.3 gum 22G H CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 H 4-OCF.sub.3 gum 23G Cl CH.sub.3 CH.sub.3
CH.sub.3 CH.sub.3 3-Cl 4-SO.sub.2 C.sub.2 H.sub.5 gum 24G H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-C(O)CH.sub.3 gum 25G H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2CH.sub.3 129-131
26G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 89-92 27G H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 115-125 28G H
CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CN 87-95
__________________________________________________________________________
.sup.a) prepared in Example 1G,G'.
Herbicidal Screening Tests
As previously mentioned, the herein described compounds produced in
the above-described manner are phytotoxic compounds which are
useful and valuable in controlling various plant species. Selected
compounds of this invention were tested as herbicides in the
following manner.
Pre-emergence herbicide test. On the day preceding treatment, seeds
of eight different weed species are planted in loamy sand soil in
individual rows using one species per row across the width of a
flat. The seeds used are green foxtail (FT) (Setaria viridis),
watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena
fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf
(VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea),
redroot pigweed (PW) (Amaranthus retroflexus) or curly dock (CD)
(Rumex crispus), and yellow nutsedge (YNG) (Cyperus esculentus).
Ample seeds are planted to give about 20 to 40 seedlings per row,
after emergence, depending upon the size of the plants.
Using an analytical balance, 600 milligrams (mg) of the compound to
be tested are weighed out on a piece of glassine weighing paper.
The paper and compound are placed in a 60 milliliter (ml)
wide-mouth clear bottle and dissolved in 45 ml of acetone or
substituted solvent. Eighteen ml of this solution are transferred
to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a
water and acetone mixture (19:1) containing enough polyoxyethylene
sorbitan monolaurate emulsifier to give a final solution of 0.5%
(v/v). The solution is then sprayed on a seeded flat on a linear
spray table calibrated to deliver 80 gallons per acre (748 L/ha).
The application rate is 4 lb/acre (4.48 Kg/ha).
After treatment, the flats are placed in the greenhouse at a
temperature of 70.degree. to 80.degree. F. and watered by
sprinkling. Two weeks after treatment, the degree of injury or
control is determined by comparison with untreated check plants of
the same age. The injury rating from 0 to 100% is recorded for each
species as percent control with 0% representing no injury and 100%
representing complete control.
The results of the tests are shown in the following Tables.
TABLE II-A
__________________________________________________________________________
Pre-Emergence Herbicidal Activity Application Rate - 4.48 kg/ha
Cmpd. No. FT WG WO AMG VL MD PW CD YNS
__________________________________________________________________________
1A 100 90 20 40 65 50 35 80 2A 80 90 0 30 80 90 20 90 3A 0 0 0 40
40 40 0 0 4A 100 100 50 35 100 100 90 95 5A 100 95 65 35 90 85 50
95 6A 50 25 0 25 100 100 35 80 7A 80 90 10 60 100 100 100 80 8A 95
95 45 40 100 80 95 95 9A 95 100 55 30 100 90 100 95 10A 100 100 60
20 85 100 100 95 11A 85 100 30 40 100 100 100 95 12A 85 85 90 75 80
95 90 90 13A 85 75 10 10 85 65 95 90 14A 40 10 80 0 65 40 65 100
15A 40 60 20 30 100 30 75 95 16A 80 80 20 55 75 90 40 95 17A 20 --
10 25 100 95 85 90 18A 65 -- 30 70 100 100 85 90 19A 45 60 0 30 40
0 20 60 20A 30 85 20 40 95 85 40 45 21A 80 100 0 80 100 100 95 95
22A 20 10 0 20 75 30 45 10 23A 45 95 10 0 100 85 100 95 24A -- 100
0 25 70 90 -- 100 25A -- 100 25 80 100 100 -- 100 26A 40 15 0 0 0
10 0 30 27A 40 80 10 20 60 50 30 75 28A 65 75 0 65 100 95 75 55 29A
100 95 55 10 80 75 85 95 30A 20 20 20 10 40 40 50 20 31A 75 95 20
20 100 95 75 10 32A 90 85 20 0 100 85 75 30 33A 80 70 0 40 20 40 90
80 34A 60 40 0 20 95 100 100 60 35A 0 10 0 0 10 20 20 10 36A 0 0 0
20 100 100 100 0 37A 40 0 0 20 100 60 90 -- 38A 10 40 0 20 90 80 20
20 39A 80 10 0 0 0 0 0 90 40A 60 0 0 0 0 0 0 90 41A 100 100 85 40
95 100 100 100 42A 60 100 25 0 0 0 0 25 43A 100 100 45 40 80 90 90
100 44A 90 100 0 60 100 100 100 95 45A 100 100 0 60 100 100 100 100
46A 20 60 0 100 100 100 100 20 47A 60 70 20 100 100 100 100 60 48A
60 0 0 0 0 0 0 40 49A 100 100 50 10 60 20 90 100 50A 100 100 80 10
60 60 90 100 51A 100 100 90 100 100 100 85 100 52A 100 100 60 10
100 100 60 100 53A 0 20 0 0 20 20 0 10 54A 10 45 10 0 0 0 0 40 55A
90 100 60 100 100 100 90 100 56A 40 70 40 40 40 60 70 50 57A 100
100 90 100 100 100 85 100 58A 90 95 0 20 20 40 40 100 59A 95 100 85
75 100 100 90 98 60A 95 100 50 50 100 100 90 98 61A 100 100 75 100
100 100 95 95 62A 100 100 95 75 100 100 100 80 63A 100 100 40 65
100 100 100 95 64A 100 100 98 100 100 100 100 90 65A 100 100 80 100
100 100 100 90 66A 100 100 75 100 100 100 100 98 73A 100 100 60 80
100 100 75 90 74A 100 100 70 80 100 100 80 100 75A 70 100 0 50 100
100 100 80 76A 40 90 25 10 100 100 100 10 77A 100 100 90 100 100
100 85 -- 78A 100 100 80 100 100 100 90 -- 79A 50 100 50 50 95 100
100 60 80A 0 0 0 0 0 0 0 0 81A 100 100 50 15 100 100 90 100 84A 100
100 85 0 0 100 20 100 88A 60 95 35 95 100 100 95 80 89A 75 100 40
100 100 100 95 60 90A 100 100 90 100 100 100 100 85 105A 80 95 25 0
95 50 70 50 117A 95 100 0 25 100 100 50 95 118A 100 100 60 100 100
100 100 85 121A 95 100 50 75 100 95 100 80 125A 100 100 50 80 100
100 100 85 126A 70 100 80 80 100 100 100 80 127A 100 100 100 100
100 100 -- 80 128A 100 100 100 100 100 100 -- 80 129A 100 100 95 90
100 100 -- 80 131A 70 85 0 20 95 98 95 90 132A 100 100 95 90 100
100 -- 80 133A 100 100 100 100 100 100 -- 80 135A 100 100 100 80
100 100 -- 80
__________________________________________________________________________
TABLE II-B ______________________________________ Pre-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1B 0 85
10 75 100 80 80 75 2B 90 100 65 100 100 100 100 100 4B 100 100 80
60 100 80 90 100 5B 80 100 20 40 100 100 80 100 6B 40 100 0 40 100
100 80 100 7B 100 100 100 80 100 100 90 100 8B 100 100 60 45 60 60
80 100 9B 60 100 40 20 60 60 60 100 10B 100 100 40 5 80 60 80 100
11B 100 100 90 10 20 20 40 100 12B 0 20 0 0 10 20 10 0 13B 100 100
90 40 100 100 100 100 15B 90 90 50 20 -- 100 100 80 16B 100 100 95
100 100 100 90 100 17B 100 100 100 100 100 100 100 97 18B 100 100
85 100 100 100 90 95 19B 100 100 95 100 100 100 100 95 20B 100 100
85 100 100 100 100 90 21B 100 100 100 100 100 100 100 95 22B 100
100 80 100 100 100 100 90 25B 100 100 75 80 100 100 100 90 26B 100
100 65 30 100 100 100 90 27B 20 95 60 5 100 100 90 100 28B 100 100
80 20 90 40 80 100 29B 100 100 70 20 100 100 100 100 30B 100 100 80
60 100 100 80 100 31B 80 100 40 10 60 60 80 100 32B 20 40 10 0 --
60 100 60 33B 0 10 0 0 10 10 0 0 34B 100 100 90 80 100 100 90 100
35B 100 100 90 40 90 90 90 90 36B 100 100 85 0 95 85 95 90 37B 90
90 50 20 -- 100 100 80 39B 15 100 0 50 100 80 70 40 40B 0 10 0 0 10
10 0 0 41B 0 20 0 0 10 20 10 0 42B 100 100 90 45 100 100 65 100 43B
100 100 90 100 100 100 100 90 44B 100 100 85 100 100 100 100 95 45B
65 100 0 0 100 20 20 90 46B 100 100 0 20 100 100 98 85 47B 100 100
90 85 100 100 100 95 48B 100 100 85 15 100 100 85 95 49B 100 100 65
0 100 100 50 50 50B 80 80 55 0 98 55 80 65 51B 95 95 10 0 65 0 25
60 52B 100 100 100 100 100 100 100 50 53B 100 100 75 100 100 100
100 50 54B 100 100 60 15 100 100 100 80 55B 100 100 55 15 100 100
90 95 56B 100 100 60 20 95 100 90 10 57B 5 10 0 0 40 20 0 0 58B 10
40 10 10 95 40 100 80 59B 100 100 75 80 100 100 100 75 60B 100 100
90 100 100 100 85 -- 61B 100 100 80 100 100 100 100 -- 62B 95 100
50 95 100 100 85 -- 63B 100 100 70 100 90 100 100 -- 64B 100 100 75
100 100 100 85 -- 65B 100 100 55 40 100 100 90 70 66B 100 100 65 35
100 100 100 95 67B 100 100 30 15 100 100 95 90 71B 100 100 80 100
100 100 80 -- 72B 100 100 40 100 100 100 90 75 73B 90 100 40 100
100 100 95 50 74B 100 100 85 95 100 100 90 80 75B 100 100 100 70
100 100 100 95 77B 100 100 55 40 100 100 90 70 81B 90 95 60 10 25
75 90 0 82B 40 90 20 35 100 -- 75 20 91B 100 100 85 100 100 100 80
90 101B 85 90 0 0 95 50 50 75
______________________________________
TABLE II-C ______________________________________ Pre-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1C 65 80
65 55 90 90 35 0 ______________________________________
TABLE II-D ______________________________________ Pre-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1D 100
100 85 30 100 100 90 90 2D 100 100 100 50 100 100 95 95 3D 100 100
85 25 100 100 100 95 4D 100 100 100 20 100 85 95 90 5D 100 100 45
25 100 100 90 90 6D 100 100 95 40 100 100 85 90 9D 100 100 90 90
100 100 80 90 10D 100 90 20 10 100 70 100 90 11D 90 100 50 230 100
100 90 90 12D 100 100 95 80 100 100 90 90 13D 40 75 0 10 80 100 100
90 14D 50 0 0 0 100 80 70 90 15D 65 95 20 15 100 80 90 85 17D 100
100 60 30 100 100 90 35 18D 100 100 100 100 100 100 100 95 19D 100
100 0 50 100 100 100 95 20D 75 100 0 25 100 90 65 90 21D 100 100
100 80 100 100 90 95 22D 100 100 100 80 100 100 95 95 23D 100 100
98 95 100 100 100 95 25D 100 100 80 100 100 100 80 -- 26D 100 100
75 100 100 100 80 -- 27D 90 100 50 100 100 100 100 90 28D 75 50 50
0 100 100 90 65 30D 100 100 85 100 100 100 95 90 31D 85 75 0 25 100
25 0 35 32D 83 85 35 20 95 100 75 50 36D 100 100 50 100 100 100 100
75 37D 20 75 0 20 100 95 100 75 38D 85 95 40 60 100 100 75 85 39D
85 95 45 75 100 95 70 90 51D 60 60 35 0 25 0 0 30 52D 75 75 0 50 90
75 40 0 65D 100 100 80 100 100 100 -- 80
______________________________________ A blank (--) indicates that
the weed was not tested.
TABLE II-E ______________________________________ Pre-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1E 0 0 0
0 0 0 0 20 2E 25 30 30 0 70 0 40 30 3E 25 20 0 0 0 0 0 0 4E 100 100
90 60 100 100 100 90 5E 50 60 40 50 50 60 90 50 6E 100 95 50 40 40
60 99 70 16E 80 100 50 60 100 90 90 90 20E 100 100 30 15 100 100 90
85 21E 100 100 -- 30 100 95 100 80
______________________________________ A blank (--) indicates that
the weed was not tested.
TABLE II-F ______________________________________ Pre-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1F 40 20
0 0 0 0 0 100 2F 60 70 0 0 0 0 90 100 3F 100 100 50 50 100 100 85
90 4F 100 100 90 30 100 85 95 95 5F 100 100 80 10 100 100 100 95 6F
20 35 25 15 90 85 40 85 7F 100 100 90 100 100 100 100 95 8F 100 100
90 100 100 100 100 95 9F 100 100 0 0 100 80 100 90 10F 100 100 100
100 100 100 100 95 11F 100 100 70 100 100 100 97 95 12F 100 100 60
100 100 100 100 95 13F 100 100 60 100 100 100 100 95 14F 80 100 50
80 100 100 90 90 15F 100 100 80 100 100 100 100 -- 16F 50 75 0 25
100 100 95 60 17F 100 100 40 100 100 100 100 85 18F 100 100 0 20
100 100 80 70 20F 70 75 0 25 100 95 100 60 21F 50 60 0 0 100 80 80
60 22F 100 95 35 25 100 100 90 50 23F 95 100 40 20 100 100 90 50
24F 100 100 90 0 45 85 80 90 25F 100 100 25 60 100 100 100 75 34F
35 40 10 0 60 25 0 70 37F 50 60 0 0 60 0 50 0 38F 35 40 0 0 0 0 0 0
52F 85 100 30 95 100 100 -- 80 53F 100 100 0 85 100 100 -- 80 54F
100 100 90 25 100 100 -- 80 ______________________________________
A blank (--) indicates that the weed was not tested.
TABLE II-G ______________________________________ Pre-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD YNS ______________________________________ 1G 100 100
90 100 100 100 80 2G 100 100 90 100 100 100 80 3G 100 100 90 100
100 100 80 4G 100 100 90 100 100 100 80 5G 100 100 90 100 100 100
80 6G* 100 100 100 100 100 -- 20 7G 100 100 80 100 100 100 80 8G 85
100 80 100 100 100 80 9G 100 100 80 100 100 100 80 10G 100 100 80
100 100 100 80 11G 100 100 80 100 100 100 80 12G 100 100 80 90 100
100 0 13G 100 100 70 100 100 100 0 14G 100 100 75 100 100 100 90
15G 100 100 80 100 100 100 90 16G 100 100 90 100 100 100 80 17G 100
100 80 100 100 100 80 18G 100 100 90 85 100 100 80 19G 100 100 100
100 100 100 80 20G 70 95 10 100 100 100 0 21G 100 100 100 100 100
100 80 22G 100 100 90 100 100 100 80 23G 100 100 100 100 100 100 80
24G 0 80 0 25 80 70 0 25G 100 100 80 100 100 100 80 26G 100 100 100
80 100 100 80 27G 100 100 100 100 100 100 80 28G 100 100 90 100 100
100 80 ______________________________________ A blank (--)
indicates that the weed was not tested. *Tested at 0.56 kg/ha.
Post-Emergence Herbicide Test: This test is conducted in an
identical manner to the testing procedure for the pre-emergence
herbicide test, except the seeds of the eight different weed
species are planted 10-12 days before treatment. Also, watering of
the treated flats is confined to the soil surface and not to the
foliage of the sprouted plants.
The results of the post-emergence herbicide test are reported in
Table III.
TABLE III-A
__________________________________________________________________________
Post-Emergence Herbicidal Activity Application Rate - 4.48 kg/ha
Cmpd. No. FT WG WO AMG VL MD PW CD YNS
__________________________________________________________________________
1A 60 70 20 40 60 60 35 60 2A 30 70 0 50 90 85 30 80 3A 0 30 0 70
100 90 55 70 4A 95 98 20 98 100 100 30 95 5A 80 80 75 50 60 80 0 95
6A 40 40 10 60 100 100 75 65 7A 60 75 40 60 100 75 100 75 8A 85 80
75 70 95 80 90 90 9A 85 80 75 70 95 80 90 90 10A 95 85 90 60 95 95
80 95 11A 50 80 35 55 100 100 95 80 12A 45 75 50 55 75 60 50 80 13A
30 60 20 60 80 50 60 70 14A 20 10 20 50 45 40 40 0 15A 65 95 0 65
95 30 100 80 16A 65 80 20 85 85 30 30 80 17A 75 80 30 70 100 100 85
90 18A 100 95 10 100 100 100 100 90 19A 60 80 40 70 100 75 80 90
20A 65 80 10 85 95 95 100 70 21A 30 55 0 80 100 80 65 80 22A 0 30 0
20 45 0 30 20 23A 85 90 40 85 100 95 100 90 24A 0 80 0 70 90 74 --
100 25A 100 100 75 90 100 100 -- 100 26A 45 30 0 40 70 65 0 45 27A
75 80 30 65 50 45 85 85 28A 75 60 60 75 100 70 80 25 29A 85 85 85
75 85 65 65 85 30A 75 50 20 10 0 0 20 40 31A 60 60 20 40 40 70 100
40 32A 60 25 20 40 90 65 20 40 33A 10 0 0 10 10 10 100 40 34A 10 10
0 5 50 30 80 0 35A 0 0 0 10 60 30 40 0 36A 0 0 0 20 20 20 0 0 37A 0
0 0 30 40 20 80 0 38A 10 10 10 20 10 20 20 10 39A 40 40 20 0 0 0 5
80 40A 90 70 40 20 60 80 20 65 41A 60 85 85 20 40 60 100 100 42A 60
50 40 70 20 40 60 60 43A 100 80 30 60 100 100 80 100 44A 80 85 0 60
90 90 100 80 45A 90 90 10 100 100 100 100 90 46A 80 100 0 60 100
100 100 100 47A 100 100 0 60 100 100 100 100 48A 40 40 20 10 10 10
90 40 49A 40 40 40 80 100 100 60 60 50A 80 60 60 50 50 60 80 70 51A
80 80 80 95 100 100 100 90 52A 60 60 20 20 40 40 90 60 53A 10 20 20
0 0 0 0 20 54A 20 40 20 5 0 0 0 40 55A 40 40 40 60 60 60 80 90 56A
100 100 75 80 100 100 100 90 57A 80 80 80 95 100 100 100 90 58A 60
70 10 70 10 10 20 80 59A 100 100 90 100 -- 100 100 50 60A 100 100
100 100 -- 100 100 70 61A 90 85 90 85 -- 100 100 80 62A 100 85 100
75 100 100 100 35 63A 70 80 20 100 100 100 35 40 64A 75 75 90 70 90
70 40 40 65A 100 70 100 55 90 95 100 40 66A 100 75 100 90 95 95 100
20 73A 100 100 95 100 100 100 55 30 74A 100 95 75 100 100 100 85 40
75A 100 100 30 95 80 100 80 40 76A 80 80 75 75 100 95 95 25 77A 80
80 80 90 90 80 90 80 78A 80 85 75 85 80 95 100 50 79A 50 65 35 90
100 100 90 -- 80A 40 40 10 20 60 0 0 30 81A 90 70 60 40 60 60 90 70
84A 100 100 100 20 40 40 80 60 88A 100 95 90 100 85 100 100 50 89A
100 100 75 85 75 85 95 50 90A 100 85 90 90 85 90 100 55 91A 100 100
100 100 95 100 95 60 105A 35 50 -- 35 100 80 60 30 117A 40 60 0 25
50 50 80 -- 118A 95 85 85 100 100 90 80 80 121A 65 85 40 100 100
100 60 50 125A 90 95 75 70 100 90 100 60 126A 40 50 20 40 60 50 100
80 127A 100 95 100 95 100 100 80 128A 85 95 80 60 100 95 80 129A 65
90 60 60 100 98 70 130A 100 95 95 95 100 100 70 131A 0 20 0 0 30 75
10 0 132A 95 100 100 80 95 95 50 133A 80 95 90 60 85 85 60 135A 70
100 100 75 100 95 70
__________________________________________________________________________
TABLE III-B ______________________________________ Post-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1B 85 95
20 95 100 100 95 95 2B 90 90 80 100 90 90 -- 80 4B 60 60 90 40 60
60 90 70 5B 40 60 10 20 40 40 90 80 6B 40 50 10 60 20 20 60 50 7B
80 80 80 60 60 90 6 60 8B 100 80 60 30 80 80 80 80 9B 70 70 60 40
60 60 80 70 10B 40 40 60 30 60 60 90 60 11B 80 90 60 45 90 90 100
80 12B 25 45 10 20 20 20 60 45 13B 100 100 95 70 60 60 80 60 15B
100 60 50 80 90 90 40 60 16B 60 60 80 80 90 90 60 65 17B 100 70 90
100 -- 90 98 70 18B 100 85 100 85 -- 100 100 65 19B 100 80 85 100
100 90 100 70 20B 90 65 90 85 70 60 100 40 21B 40 40 10 0 0 0 0 0
22B 40 70 80 90 90 100 95 40 25B 40 70 40 40 40 60 70 50 26B 65 70
80 40 90 80 70 80 27B 100 80 60 20 90 90 80 45 28B 90 60 60 60 60
60 40 70 29B 90 70 70 40 70 70 60 60 30B 100 90 70 50 100 100 80 80
31B 40 50 20 10 20 20 0 40 32B 25 40 40 90 100 100 40 40 33B 20 40
10 60 90 90 60 40 34B 90 80 80 80 100 100 80 50 35B 60 50 50 20 60
60 80 60 36B 100 80 80 75 -- 100 100 45 37B 100 60 50 80 90 90 40
60 39B 90 80 25 30 30 45 50 30 40B 20 40 10 60 90 90 60 40 41B 25
45 10 20 20 20 60 45 42B 90 80 80 80 100 100 100 70 43B 80 90 95 97
100 100 100 50 44B 100 95 95 95 40 100 100 30 45B 30 65 0 30 45 40
65 50 46B 70 75 0 65 100 100 50 70 47B 100 100 100 90 100 100 100
85 48B 100 65 80 50 100 100 60 60 49B 60 70 70 40 80 70 30 50 50B 0
60 40 60 100 90 20 30 51B 100 75 80 40 100 50 20 30 52B 90 100 100
100 100 100 100 40 53B 60 70 70 70 90 65 40 60 54B 100 100 85 100
100 100 100 60 55B 95 85 90 100 100 100 90 45 56B 85 100 0 10 15 95
40 50 57B 85 70 65 0 0 0 0 35 58B 20 40 10 15 70 40 35 40 59B 100
95 100 95 100 95 100 40 60B 65 75 75 80 90 85 80 60 61B 80 80 70 95
80 85 80 50 62B 100 80 25 80 75 80 85 35 63B 100 100 40 95 95 100
95 50 64B 75 70 50 90 90 100 90 50 65B 100 80 80 60 85 60 0 -- 66B
98 90 60 35 -- 100 60 90 67B 70 65 20 15 95 40 70 45 71B 95 50 50
80 80 80 65 50 72B 100 85 75 75 65 85 70 60 73B 100 95 95 85 75 85
95 40 74B 100 85 95 90 80 95 65 50 75B 100 80 80 30 50 60 100 40
81B 50 80 35 70 70 90 80 10 82B 25 60 50 35 50 90 50 25 91B 80 60
40 60 75 90 60 75 101B 10 35 -- 30 75 70 40 50
______________________________________ (--) = Specie did not
germinate for some reason.
TABLE III-C ______________________________________ Post-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1C 98 95
70 60 100 55 100 90 ______________________________________
TABLE III-D ______________________________________ Post-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNS ______________________________________ 1D 95 75
85 70 100 90 85 40 2D 45 70 95 75 100 90 100 65 3D 100 80 100 90 --
100 100 80 4D 100 80 100 100 -- 100 85 75 5D 90 70 45 60 95 70 60
80 6D 95 75 80 70 100 90 90 65 9D 100 90 90 100 100 100 95 85 10D
45 75 10 15 100 100 20 75 11D 100 70 60 75 100 100 100 45 12D 100
75 100 100 100 100 90 90 13D 30 55 0 30 60 60 15 60 14D 20 65 0 40
70 60 40 25 15D 20 75 30 20 100 70 60 40 17D 85 80 50 65 95 95 100
60 18D 100 95 100 100 100 100 100 75 19D 20 95 30 100 100 35 30 70
20D 30 80 15 100 100 45 20 70 21D 100 80 100 55 100 90 100 80 22D
100 80 100 60 100 95 95 95 23D 100 90 90 100 100 100 85 70 25D 70
75 50 85 90 85 60 75 26D 100 85 85 95 95 95 90 60 27D 90 90 60 100
100 100 100 -- 28D 15 45 20 50 75 80 15 30 30D 100 100 80 85 85 85
100 -- 31D 80 90 100 100 100 100 100 60 32D 75 85 85 75 75 90 95 50
36D 35 50 35 70 50 50 35 60 37D 60 75 15 70 70 90 90 40 38D 95 90
65 70 90 90 100 50 39D 95 85 30 50 70 80 100 50 51D 60 75 60 35 30
60 40 60 52D 60 75 25 100 100 100 100 75 65D 70 50 70 90 80 85 --
80 ______________________________________ A blank (--) indicates
the weed was not tested.
TABLE III-E ______________________________________ Post-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNG ______________________________________ 1E 20 20
10 20 40 40 20 40 2E 0 60 60 50 70 30 0 15 3E 20 20 0 10 0 20 0 20
4E 85 90 100 45 75 30 80 65 5E 55 50 60 50 75 85 65 -- 6E 70 70 50
60 80 70 90 -- 16E 95 95 40 100 100 100 100 90 20E 95 75 35 40 95
75 35 80 21E 80 70 30 45 80 90 50 70
______________________________________ A blank (--) indicates the
weed was not tested.
TABLE III-F ______________________________________ Post-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD CD YNG ______________________________________ 1F 60 40
20 30 40 40 50 60 2F 50 40 10 20 20 20 40 60 3F 100 100 85 100 100
100 100 75 4F 100 100 95 85 100 95 100 60 5F 95 95 100 65 90 25 70
45 6F 40 30 0 20 90 25 20 70 7F 100 100 100 100 100 100 100 90 8F
100 95 100 100 100 100 100 70 9F 65 65 0 20 80 65 90 80 10F 100 100
100 100 100 100 100 70 11F 85 90 90 85 90 80 30 60 12F 100 90 65 80
100 100 100 50 13F 100 95 100 100 100 100 90 -- 14F 100 100 100 100
100 100 100 50 15F 25 35 15 30 80 25 20 0 16F 100 85 70 75 90 90 50
-- 17F 100 100 100 100 100 100 100 -- 18F 90 85 85 85 90 95 70 40
20F 40 60 10 60 100 100 100 50 21F 35 60 10 60 100 100 80 60 22F 95
95 35 100 100 100 90 50 23F 100 100 40 100 100 100 90 50 24F 100 75
100 60 -- 100 100 60 25F 95 95 90 95 100 100 95 35 34F 50 40 0 35
50 70 30 50 37F 20 60 0 30 30 50 50 50 38F 25 50 0 25 25 50 20 20
52F 0 60 50 50 10 50 -- 20 53F 0 50 0 50 50 50 -- 30 54F 90 75 60
50 50 80 -- 80 ______________________________________ A blank (--)
indicates the weed was not tested.
TABLE III-G ______________________________________ Post-Emergence
Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. No. FT WG
WO AMG VL MD YNG ______________________________________ 1G 100 95
90 90 100 100 80 2G 100 100 100 100 100 100 80 3G 100 100 95 100
100 100 90 4G 100 100 100 100 100 100 90 5G 100 100 100 100 100 100
100 6G* 10 80 50 75 40 -- 0 7G 70 75 70 90 90 80 80 8G 50 80 70 90
90 80 30 9G 70 80 70 90 90 80 30 10G 75 80 70 80 60 50 70 11G 70 80
70 80 80 80 80 12G 100 75 90 75 80 80 80 13G 60 70 70 100 100 100
80 14G 20 70 40 60 80 80 70 15G 90 70 70 75 80 90 70 16G 50 70 80
60 80 90 70 17G 90 60 70 65 80 80 80 18G 30 50 80 95 95 80 70 19G
100 100 95 90 100 100 80 20G 10 40 5 70 80 90 70 21G 95 90 95 95
100 100 70 22G 80 90 90 80 100 100 70 23G 90 80 80 80 90 80 30 24G
0 30 0 40 80 20 0 25G 0 20 0 10 10 20 0 26G 80 70 70 80 80 80 70
27G 90 90 90 80 80 90 60 28G 70 65 50 80 80 80 70
______________________________________ A blank (--) indicates the
weed was not tested. *Tested at 0.56 kg/ha.
Pre-Emergence Multi-Weed Herbicide Test
Several compounds were evaluated at an application rate of 2
lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for pre-emergence
activity against a larger number of weed species.
The process was generally similar to the pre-emergence herbicide
test described above except that only 300 or 150 milligrams of test
compound were weighed out and the application rate was 40 gallons
per acre.
Redroot pigweed (PW) and curly dock (CD) were eliminated in this
test and the following weed species were added:
______________________________________ Grasses: downy brome Bromus
tectorum (DB) annual ryegrass Lolium multiflorum (ARG) rox-orange
sorghum Sorghum bicolor (SHC) hemp sesbania Sesbania exaltata
(SESB) nightshade Solanum sp. (SP) cocklebur Xattiium sp. (CB)
______________________________________
The results of the 2.24 kg/ha test are shown in Table IV and the
results of the 1.12 kg/ha test are shown in Table VI.
Post-Emergence Multi-Weed Herbicide Test
Several compounds were evalated at an application rate of 2 lb/acre
(2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for post-emergence activity
against the larger number of weed species that are used in the
pre-emergent multi-herbicide test.
The process was generally similar to the post-emergence herbicide
test describe above except that only 300 or 150 milligrams of test
compound were weighed out and the application rate was 40 gallons
per acre.
The results of the 2.24 kg/ha test are shown in Table V and the
results for the 1.12 kg/ha test are shown in Table VII.
TABLE IV-A
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate - 2.24
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
67A 20 90 25 98 80 60 90 45 90 45 20 85 85 15 68A 65 98 98 100 100
60 95 100 100 100 80 100 95 100 69A 65 100 70 100 100 65 95 100 95
70 65 100 90 -- 70A 98 100 100 100 100 90 98 90 100 90 60 100 95 80
71A 60 20 100 100 100 80 95 35 40 100 20 90 100 40 72A 100 100 100
100 100 100 100 100 90 100 60 100 100 20 83A 15 45 25 90 15 5 90 45
35 20 0 20 75 -- 86A 20 0 15 60 60 20 70 25 45 100 20 100 15 35 87A
100 90 85 100 85 25 30 35 85 100 85 100 95 40
__________________________________________________________________________
TABLE VI-A
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test Application Rate - 2.24
hg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
86A 60 100 50 90 50 60 90 70 100 100 20 100 20 -- 87A 95 100 30 100
80 70 80 95 100 100 100 100 70 --
__________________________________________________________________________
TABLE V-A
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate - 1.12
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
82A 35 100 85 100 65 60 90 50 90 60 30 97 90 40 85A 100 100 100 100
100 85 100 20 10 100 65 100 100 30 92A 15 20 45 100 90 40 80 95 95
100 25 100 90 40 93A 30 75 40 100 100 60 90 100 100 100 35 100 90
40 94A 30 70 40 100 100 30 65 95 85 100 0 100 90 30 95A 0 0 0 85 60
15 70 65 60 100 80 90 10 20 96A 95 100 98 100 100 70 100 100 95 90
80 100 95 -- 97A 100 100 98 100 100 100 100 100 95 100 70 100 95
100 98A 10 0 0 0 20 25 70 0 20 0 0 80 30 -- 99A 15 0 0 75 25 0 20
30 60 15 20 30 25 0 100A 0 0 0 0 0 0 20 10 0 0 0 15 0 -- 101A 100
98 95 100 100 70 98 100 100 100 20 100 95 -- 102A 25 20 35 100 100
45 95 70 100 100 60 100 90 -- 103A 80 60 45 100 100 40 90 65 90 100
0 100 95 0 106A 100 100 60 40 95 35 100 35 90 100 70 100 90 -- 107A
100 100 100 100 100 90 100 100 100 100 80 100 95 30 108A 100 100
100 100 100 85 100 100 100 100 30 100 95 100 109A.sup.a 65 20 85
100 98 60 90 30 50 100 50 100 90 100 110A 0 60 30 100 65 25 65 25
30 100 0 100 60 0 111A 100 100 100 100 100 75 98 100 100 100 90 100
-- 70 112A 100 100 90 100 100 95 100 100 100 100 100 100 -- -- 113A
65 95 40 100 100 30 90 70 100 100 0 100 -- 30 114A 70 100 25 100
100 40 100 100 100 100 30 100 95 80 115A 100 100 100 100 100 100
100 100 100 100 45 100 85 100 116A 25 15 20 100 65 35 65 45 50 100
0 100 95 10 119A 100 100 100 100 100 100 100 100 100 100 95 100 95
90 120A 100 100 100 100 100 95 100 100 100 100 100 100 90 100 122A
80 80 45 100 60 65 70 100 100 100 100 100 90 100 123A 0 100 50 100
85 0 60 100 90 100 80 100 100 20 124A 25 50 65 90 65 0 40 75 80 100
40 90 80 60
__________________________________________________________________________
.sup.a application rate was 0.56 kg/ha.
TABLE VII-A
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test Application Rate - 1.12
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
82A 60 40 10 98 35 10 30 70 100 100 100 90 45 -- 85A 60 60 35 100
45 60 85 50 100 100 100 100 60 -- 92A 70 55 20 80 80 45 100 95 90
80 20 95 70 90 93A 90 90 70 95 95 75 90 98 95 85 35 100 60 90 94A
100 85 45 90 100 90 100 100 90 90 30 100 60 85 95A 20 60 0 80 70 0
45 60 75 90 0 65 20 -- 96A 95 100 90 95 100 80 95 100 100 100 70
100 70 90 97A 100 100 95 100 100 100 100 100 100 100 90 100 70 100
98A 20 0 0 45 10 50 30 20 65 100 0 75 35 80 99A 25 75 15 80 65 10
25 85 100 100 80 100 10 -- 100A 10 35 0 70 50 5 20 30 70 40 0 100
10 100 101A 30 60 25 100 60 60 80 100 100 100 30 100 70 -- 103A 90
100 25 100 100 80 100 100 100 100 15 100 40 -- 104A 98 98 25 98 100
15 100 100 100 100 60 100 95 -- 106A 75 90 30 90 70 25 100 100 100
100 80 100 75 -- 107A 100 100 80 90 85 100 100 100 100 100 60 100
40 -- 108A 100 100 65 90 60 95 100 100 100 100 90 100 90 --
109A.sup.a 90 60 45 90 70 60 98 95 95 100 98 80 55 -- 110A 50 50 20
100 50 10 40 100 98 98 20 100 35 45 111A 85 90 80 90 70 60 95 100
90 100 65 100 80 60 112A 100 100 90 100 100 95 100 100 100 100 45
100 95 70 113A 70 50 20 90 60 50 80 95 95 100 60 100 -- 60 114A 85
100 15 100 100 60 00 100 100 100 100 100 60 -- 115A 100 100 45 100
100 80 100 100 100 100 100 100 90 -- 116A 80 60 25 90 35 40 45 75
90 100 40 90 75 60 119A 60 70 30 95 70 20 90 100 100 100 90 100 30
85 120A 75 90 60 95 80 45 100 100 90 100 65 100 35 100 122A 60 90
15 100 30 15 15 100 100 100 75 100 45 95 123A 0 100 35 100 50 15 85
100 100 100 100 100 70 85 124A 25 100 35 40 35 0 40 95 100 100 100
100 85 75
__________________________________________________________________________
A = Application rate was 0.56 kg/ha. A dash mark (--) is used in
Tables II-VII to indicate that no percent control number was
available.
TABLE IV-B
__________________________________________________________________________
Pre-Emergence Multi-Weed Herbicide Test Application Rate - 2.24
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
14B 80 100 100 100 100 80 95 70 60 100 40 85 100 10 21B 85 100 90
100 100 85 100 100 100 100 70 100 95 100 24B 100 100 100 100 100
100 100 100 100 100 75 100 95 -- 38B 100 100 100 100 100 100 100 20
10 100 20 95 100 20 88B 75 100 60 100 100 70 60 20 40 100 0 100 60
20 89B 20 60 30 85 95 55 40 15 20 65 0 100 35 50 90B 60 100 60 100
100 45 30 100 100 100 15 100 50 85 103B 95 100 75 100 100 50 85 100
100 100 80 100 80 40 104B 60 100 60 100 100 45 30 100 100 100 15
100 50 85
__________________________________________________________________________
(--) = Specie did not germinate for some reason.
TABLE V-B
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicide Test Application Rate - 2.24
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
24B 35 25 45 60 65 85 90 100 100 -- 90 100 65 -- 88B 60 30 30 90
100 80 100 100 100 100 30 100 20 100 89B 50 70 35 90 60 35 20 100
90 100 35 100 15 100 90B 30 100 40 100 70 10 25 100 100 100 30 90
50 95 103B 95 100 70 100 65 75 65 100 100 100 65 100 50 100 104B 30
100 40 100 70 10 25 100 100 100 30 90 50 95
__________________________________________________________________________
(--) = Specie did not germinate for some reason.
TABLE VI-B
__________________________________________________________________________
Pre-Emergence Multi-Weed Herbicide Test Application Rate - 1.12
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
1B 25 10 30 85 55 0 -- 55 -- 100 -- 75 75 35 23B 55 95 90 100 95*
95 95 98 80 -- 10 100 95 -- 68B 65 100 60 100 100* 6 90 100 90 100
20 100 30 40 69B 70 100 60 100 100* 95 95 100 95 100 0 100 85 25
70B 60 100 75 100 100* 85 100 100 90 100 25 100 90 25 76B 100 100
85 100 100* 85 98 100 95 -- 35 100 95 78B 40 70 15 95 75* 25 80 65
75 -- 0 100 80 -- 79B 100 100 100 100 100 98 100 100 85 100 85 100
95 -- 80B 98 100 95 100 100 60 98 99 90 100 35 100 85 -- 83B 20 100
60 100 100* 40 90 85 65 100 0 100 85 -- 84B 0 90 25 98 100* 30 90
20 35 100 5 100 50 -- 85B 80 100 50 100 100 60 90 100 90 100 0 100
95 -- 86B 60 90 40 100 100 60 70 35 60 100 100 100 -- -- 87B 0 90
15 100 85 15 70 40 60 100 40 90 20 -- 92B 20 40 10 95 40 10 60 65
30 100 0 55 60 0 93B 60 95 20 100 100 75 100 100 100 100 0 100 40
35 94B 0 80 40 100 95 25 85 80 40 100 10 85 55 10 95B 98 100 30 100
100 40 90 100 100 100 40 100 90 30 96B 100 100 75 100 100 95 100
100 100 100 60 100 85 100 97B 100 100 90 100 100 95 100 100 100 100
60 100 95 100 98B 95 100 100 100 100 80 100 100 100 100 50 100 100
60 99B** -- 100 75 100 100* 20 75 50 75 95 0 -- 85 30 100B 100 98
98 100 100 90 95 100 75 100 70 100 95 40 102B 0 100 25 100 90 75 95
60 60 100 30 100 90 --
__________________________________________________________________________
*seedling johnsongrass (Sroghum halepense) was substituted for
roxorgange sorghum. **Application rate was 0.56 kg/ha (--) = Specie
did not germinate for some reason.
TABLE VII-B
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicide Test Application Rate - 1.12
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
1B 45 35 40 90 35 10 -- 60 -- 75 -- 60 50 55 23B 90 100 80 90 90*
90 90 80 90 90 40 70 25 -- 68B 50 60 40 85 80* 75 100 95 90 85 55
100 40 -- 69B 70 80 35 90 90* 80 90 80 85 90 20 90 25 -- 70B 100 90
80 100 100* 95 100 100 95 80 30 75 45 90 76B 100 100 98 100 100*
100 100 100 100 100 60 100 40 -- 78B 100 90 80 85 100* 70 90 100
100 100 0 90 45 -- 79B 80 35 45 70 60* 70 70 45 98 100 35 90 20 --
80B 60 70 25 90 60* 60 85 70 90 100 15 100 25 100 85B 95 100 65 100
80 90 100 100 100 100 25 100 85 -- 86B 30 60 20 75 50 50 60 50 65
100 10 100 20 80 87B 0 0 0 100 45 20 30 60 90 80 0 100 30 45 92B 20
80 10 85 15 0 30 100 40 100 0 60 60 30 93B 70 100 25 100 100 85 100
100 100 100 100 100 80 -- 94B 20 70 30 90 80 30 20 100 100 100 60
30 30 100 95B 60 90 15 95 95 25 90 100 100 100 75 100 70 100 96B 50
80 0 90 70 30 100 100 100 100 40 100 20 100 97B 65 100 35 100 75 70
80 100 100 100 50 100 50 100 98B 95 100 65 95 90 100 95 100 100 90
40 80 60 95 99B** -- 100 95 90 90* 90 100 25 80 40 100 -- 35 75
100B 65 75 60 80 75 60 85 100 100 100 45 100 65 60 102B 30 75 20 80
60 0 40 70 100 100 30 100 75 --
__________________________________________________________________________
*Seedling johnsongram (Sorghum halepense) was substituted for
roxorange sorghum. **Application rate was 0.56 kg/ha. (--) = Specie
did not germinate for some reason.
TABLE IV-C
__________________________________________________________________________
Post-Emergence Multi-weed Herbicidal Test Application Rate - 1.12
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
2C 0 100 0 100 -- 45 70 65 50 100 15 100 90 --
__________________________________________________________________________
(--) = Not tested.
TABLE V-C
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity Application Rate -
1.12 kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS
CB
__________________________________________________________________________
2D 0 30 0 100 -- 0 60 85 95 100 100 90 40 --
__________________________________________________________________________
(--) = Not tested.
TABLE IV-D
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate - 2.24
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
7D 100 100 100 100 100 100 100 100 100 100 100 100 95 100 8D 100
100 100 100 100 100 100 100 100 100 100 100 95 -- 16D.sup.a 70 100
65 100 100 60 98 55 100 100 90 100 90 -- 24D 100 100 100 100 100
100 100 100 100 100 100 100 100 -- 29D 100 100 100 100 100 100 100
100 100 100 30 100 95 80 33D 75 15 60 90 90 20 95 100 100 100 60
100 95 100 53D 100 100 100 100 100 90 100 100 100 100 100 100 95
100 57D 100 100 25 100 100 30 25 100 100 100 100 100 95 100
64D.sup.a -- 0 0 95 35 0 15 50 75 75 25 -- 75 40 66D.sup.a -- 0 15
15 50 20 50 100 100 75 0 -- 90 100 67D.sup.a -- 0 0 100 100 0 25 95
75 50 25 -- 30 75 69D.sup.a -- 30 0 100 100 0 70 100 100 100 35 --
95 100 70D.sup.a -- 100 10 100 100 25 65 100 100 100 0 -- 95 100
__________________________________________________________________________
(--) = Not tested. .sup.a Tested at 0.28 kg/ha.
TABLE V-D
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate-1.12 kg/ha
Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
34D 90 85 30 95 -- 45 98 75 100 100 40 100 50 -- 35D 100 85 70 100
-- 90 100 100 100 100 40 100 75 -- 40D 100 100 20 100 -- 70 100 98
98 100 20 100 50 -- 41D 100 100 80 100 -- 60 100 100 100 100 25 100
95 -- 42D 50 60 40 85 -- 30 100 100 100 100 100 100 90 -- 43D 90 95
60 100 -- 30 98 100 98 100 45 100 95 -- 44D 60 100 20 100 -- 60 100
100 90 100 20 100 80 -- 45D 95 100 35 100 -- 60 90 100 100 100 0
100 90 -- 46D 100 100 90 100 -- 95 100 100 100 100 40 100 95 -- 47D
100 100 100 100 -- 98 100 100 98 100 30 100 95 -- 48D 100 100 100
100 -- 100 100 100 100 100 90 100 100 -- 49D 100 100 100 100 -- 100
100 100 100 100 90 100 -- -- 50D 100 100 100 100 100 85 100 100 100
100 90 100 98 -- 54D 100 100 85 100 100 15 100 25 100 100 65 100 95
100 55D 85 100 35 100 98 15 100 15 100 100 65 100 95 -- 56D 100 100
100 100 100 100 100 100 100 100 100 100 100 100 58D 98 100 40 95 40
20 95 100 100 100 85 100 100 95 59D 100 100 100 100 100 90 100 100
100 100 100 100 85 80 60D 100 100 100 100 100 100 100 100 100 100
75 100 85 80
__________________________________________________________________________
(--) = Not tested.
TABLE VI-D
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate-0.56 kg/ha
Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
61D -- 100 65 100 65 20 80 20 40 80 10 -- 20 0 62D -- 50 35 70 50 0
0 0 25 50 0 -- 0 0 63D 100 100 100 100 100 95 100 90 95 100 75 100
100 85 68D -- 0 20 0 0 0 0 60 100 100 90 -- 75 75 71D -- 50 40 50
75 40 35 75 50 70 0 -- 75 75 72D -- 35 60 100 85 50 100 25 65 100
35 -- 100 35 73D -- 90 70 100 95 25 0 70 100 100 0 -- 50 25
__________________________________________________________________________
(--) = Not tested.
TABLE VII-D
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity Application Rate-2.24
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
7D 100 100 100 100 80 90 10 95 100 100 55 100 45 100 16D.sup.a 100
85 35 100 100 100 100 100 100 100 100 100 85 70 24D 100 100 100 100
100 100 100 100 100 100 100 100 100 -- 29D 100 100 60 100 90 100
100 100 100 100 100 100 100 -- 33D 90 98 85 100 100 80 100 100 100
100 90 100 90 100 53D 100 100 60 100 100 100 100 100 100 100 100
100 100 -- 57D 25 40 10 100 10 0 10 100 95 100 35 100 -- 100
64D.sup.a -- 0 0 90 0 0 85 40 100 80 50 -- 35 100 66D.sup.a -- 0 0
65 0 0 70 75 80 75 0 -- 25 75 67D.sup.a -- 0 0 75 35 0 40 70 80 60
0 -- 0 100 69D.sup.a -- 0 0 80 35 0 100 90 100 100 40 -- 35 100
70D.sup.a -- 100 0 100 70 90 90 100 100 100 30 -- 25 100
__________________________________________________________________________
(--) = Not tested. .sup.a Tested at 0.28 kg/ha.
TABLE VIII-D
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test Application Rate-1.12
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
34D 90 85 30 95 -- 45 98 75 100 100 40 100 50 -- 35D 100 85 70 100
-- 90 100 100 100 100 40 100 75 -- 40D 75 100 5 100 -- 50 75 100
100 100 40 100 30 -- 41D-- -- -- -- -- -- -- -- -- -- -- -- -- --
-- 42D 40 100 35 100 -- 50 80 100 100 100 80 100 70 -- 43D 60 70 20
100 -- 55 60 100 100 100 95 100 70 -- 44D -- -- -- -- -- -- -- --
-- -- -- -- -- -- 45D -- -- -- -- -- -- -- -- -- -- -- -- -- -- 46D
-- -- -- -- -- -- -- -- -- -- -- -- -- -- 47D 90 100 35 100 -- 75
90 100 100 100 25 100 45 -- 48D 80 100 60 100 -- 60 80 100 100 100
85 100 60 -- 49D -- -- -- -- -- -- -- -- -- -- -- -- -- -- 50D 90
80 60 95 80 90 100 100 100 100 65 100 80 -- 54D 35 50 30 100 30 15
90 100 100 100 100 100 95 -- 55D 100 100 20 100 90 20 100 90 100
100 100 100 -- -- 56D 75 90 75 95 90 25 100 100 100 100 90 100 90
100 58D 70 100 40 100 95 30 95 100 95 100 95 100 95 85 59D 90 100
95 100 100 50 100 100 100 100 95 100 100 95 60D 95 100 100 100 100
75 95 100 100 100 95 100 100 100
__________________________________________________________________________
(--) = Not tested.
TABLE IX-D
__________________________________________________________________________
Post-Emergence Multi-weed Herbicide Test Application Rate-0.56
kg/ha Cmpd. No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
61D -- 40 0 50 35 0 40 75 95 100 0 -- 25 50 62D -- 35 0 20 0 0 20
35 60 100 0 -- 0 100 63D 100 100 85 98 85 100 100 100 100 100 100
85 85 95 68D -- 30 40 85 0 25 60 80 95 100 95 -- 0 80 71D -- 50 0
80 65 0 75 100 80 100 50 -- 25 100 72D -- 90 70 80 50 50 75 85 100
100 90 -- 100 100 73D -- 100 15 100 75 75 85 100 100 90 60 -- 80
100
__________________________________________________________________________
(--) = Not tested.
TABLE IV-E
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate-2.24 kg/ha
Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS
__________________________________________________________________________
17E 95 85 35 100 85 25 90 100 100 100 40 100 95 18E 0 0 0 50 20 0
15 60 45 100 0 100 --
__________________________________________________________________________
TABLE V-E
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate-1.12 kg/ha
Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS
__________________________________________________________________________
7E 30 70 20 100 75 0 90 100 95 100 100 100 90 8E 95 95 45 100 98 25
90 100 95 100 90 100 90 9E 10 70 40 100 20 0 80 100 85 100 40 100
95 10E 100 100 10 100 40 0 90 100 100 100 80 100 100 11E 90 100 90
100 100 65 100 100 90 100 30 100 65 12E 100 100 80 100 100 85 90
100 100 100 85 100 90 13E 0 100 10 100 100 80 70 80 90 100 70 100
80 15E 0 10 0 90 0 0 15 35 30 100 10 85 75 19E 100 90 0 100 20 10
40 95 100 100 100 100 65
__________________________________________________________________________
TABLE VI-E
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity Application Rate-2.24
kg/ha Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS
__________________________________________________________________________
17E 80 100 55 95 90 20 60 100 100 100 75 100 70 18E 0 100 0 98 20 0
10 70 60 100 10 100 45
__________________________________________________________________________
TABLE VII-E
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity Application Rate-1.12
kg/ha Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS
__________________________________________________________________________
7E 25 30 0 70 60 20 90 75 95 85 50 100 35 8E 80 80 20 70 70 40 80
50 80 80 60 60 35 9E 0 30 0 75 15 25 100 95 100 100 60 100 25 10E
60 80 20 70 35 25 80 75 90 90 70 100 45 11E 45 100 20 100 100 40 50
100 100 100 20 100 35 12E 70 60 30 100 100 80 98 90 100 100 70 98
40 13E 25 100 10 100 100 85 100 80 100 100 10 90 25 15E 30 65 10 90
50 30 20 85 80 98 30 65 15 19E 20 60 10 90 10 15 90 100 100 70 100
40 85
__________________________________________________________________________
TABLE IV-F
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate-1.12 kg/ha
Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
19F 40 35 60 100 90 30 90 100 100 -- 20 100 90 -- 26F 25 70 45 95
60 25 85 35 75 -- 20 100 95 90 27F 45 65 40 100 60 25 80 100 85 100
40 100 95 35 28F 80 100 90 100 100 90 100 70 90 100 30 100 95 35
29F 90 45 75 100 85 40 90 95 90 100 40 100 95 -- 30F 90 45 75 100
90 75 100 100 80 100 60 100 95 -- 31F 60 65 75 100 100 55 95 100
100 100 100 100 95 -- 32F 90 100 90 100 100 65 85 100 90 100 95 100
85 -- 33F 100 100 95 100 100 95 100 100 100 100 25 100 90 -- 35F 90
100 100 100 -- 90 90 100 90 100 10 100 75 -- 36F 90 35 85 100 -- 15
80 95 90 100 50 100 95 -- 39F 100 100 100 100 100 95 100 100 100
100 100 100 98 -- 40F 100 100 80 100 100 70 100 100 100 100 90 100
95 -- 41F 100 100 100 100 100 100 100 100 100 100 60 100 98 -- 42F
60 100 85 100 100 70 95 100 95 100 10 100 95 50 43F 85 100 25 100
60 25 98 100 100 100 100 100 90 100 44F 0 80 10 85 0 0 75 0 30 100
0 100 0 10 45F 25 100 40 100 60 0 65 60 60 100 50 100 70 0 50F --
100 50 100 35 35 75 100 100 --
__________________________________________________________________________
(--) = Not tested.
TABLE V-F
__________________________________________________________________________
Pre-Emergence Multi-weed Herbicide Test Application Rate-0.56 kg/ha
Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
46F 0 65 35 75 65 0 0 0 35 100 25 90 80 0 47F -- 60 35 100 100 0 90
100 100 100 70 -- 100 75 48F -- 75 20 90 60 0 15 70 35 90 0 -- 20
40 49F -- 60 10 100 60 0 50 100 95 100 40 -- 90 100 51F -- 40 10 95
40 10 50 65 100 100 0 -- 95 65
__________________________________________________________________________
(--)-Not tested.
TABLE VI-F
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity Application Rate-2.24
kg/ha Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
19F 100 90 65 100 100 98 100 100 100 100 60 100 70 100 26F 60 75 60
95 45 50 90 50 90 100 40 90 60 -- 27F 80 70 65 95 100 90 100 100
100 100 85 100 75 -- 28F 80 100 75 90 85 80 100 80 80 100 30 100 85
85 29F 85 70 55 90 98 90 100 100 100 100 35 100 60 100 30F 90 80 40
.90 85 80 80 70 100 100 20 100 40 -- 31F 100 80 20 100 100 100 100
100 100 100 100 100 85 -- 32F 70 90 60 100 100 98 100 100 100 100
100 100 60 -- 33F 95 100 80 100 90 100 100 100 100 100 70 100 40 --
35F 70 90 40 100 -- 100 100 100 100 100 98 100 30 -- 36F 85 100 35
100 -- 20 100 100 100 100 100 100 15 -- 39F 100 100 85 100 100 100
100 100 100 100 100 100 90 100 40F 100 100 30 100 100 100 100 100
100 100 90 100 75 -- 41F 100 100 35 90 70 100 90 100 100 100 50 100
70 -- 42F 45 100 50 100 70 55 80 100 100 100 70 100 75 100 43F 25
80 15 98 35 0 20 100 100 100 100 100 60 95 44F 0 15 0 65 0 0 0 70
100 100 40 100 0 100 45F 0 75 35 70 35 0 60 50 85 100 50 100 75 70
50F -- 40 0 75 45 40 60 100 100 95 30 -- 60 100
__________________________________________________________________________
(--) = Not tested.
TABLE VII-F
__________________________________________________________________________
Post-Emergence Multi-Weed Herbicidal Activity Application Rate-0.56
kg/ha Cmpd. No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB
__________________________________________________________________________
46F 25 35 20 50 35 35 0 20 75 100 35 95 -- 50 47F -- 75 25 90 40 25
80 100 100 100 80 -- 75 100 48F -- 50 35 80 35 40 0 75 100 85 15 --
50 75 49F -- 35 0 75 30 0 20 100 100 100 80 -- 25 85 51F -- 35 0 80
35 20 70 50 95 95 25 -- 65 50
__________________________________________________________________________
(--) = Not Tested.
The compounds of the present invention and their salts are useful
as herbicides and can be applied in a variety of ways at various
concentrations. In practice, the compounds or salts are formulated
into herbicidal compositions, by admixture, in herbicidally
effective amounts, with the adjuvants and carriers normally
employed for facilitating the dispersion of active ingredients for
agricultural applications, recognizing the fact that the
formulation and mode of application of a toxicant may affect the
activity of the materials in a given application. Thus, these
active herbicidal compounds or salts can be formulated as granules
of relatively large particle size, as wettable powders, as
emulsifiable concentrates, as powdery dusts, as flowables, as
solutions or as any of several other known types of formulations,
depending upon the desired mode of application. These formulations
may contain as little as about 0.5% to as much as about 95% or more
by weight of active ingredient. A herbicidally effective amount
depends upon the nature of the seeds or plants to be controlled and
the rate of application varies from about 0.01 to approximately 10
pounds per acre, preferably from about 0.02 to about 4 pounds per
acre.
Wettable powders are in the form of finely divided particles which
disperse readily in water or other dispersants. The wettable powder
is ultimately applied to the soil either as a dry dust or as a
dispersion in water or other liquid. Typical carriers for wettable
powders include fuller's earth, kaolin clays, silicas and other
readily wet organic or inorganic diluents. Wettable powders
normally are prepared to contain about 5% to about 95% of the
active ingredient and usually also contain a small amount of
wetting, dispersing, or emulsifying agent to facilitate wetting and
dispersion.
Emulsifiable concentrates are homogeneous liquid compositions which
are dispersible in water or other dispersant, and may consist
entirely of the active compound or salt with a liquid or solid
emulsifying agent, or may also contain a liquid carrier, such as
xylene, heavy aromatic naphthal, isophorone and other non-volatile
organic solvents. For herbicidal application, these concentrates
are dispersed in water or other liquid carrier and normally applied
as a spray to the area to be treated. The percentage by weight of
the essential active ingredient may vary according to the manner in
which the composition is to be applied, but in general comprises
about 0.5% to 95% of active ingredient by weight of the herbicidal
composition.
Granular formulations wherein the toxicant is carried on relatively
coarse particles, are usually applied without dilution to the area
in which suppression of vegetation is desired. Typical carriers for
granular formulations include sand, fuller's earth, attapulgite
clay, bentonite clays, montmorillonite clay, vermiculite, perlite
and other organic or inorganic materials which absorb or which may
be coated with the toxicant. Granular formulations normally are
prepared to contain about 0.1% to about 25% of active ingredients
which may include surface-active agents such heavy aromatic
naphthas, kerosene or other petroleum fractions, or vegetable oils;
and/or stickers such as dextrins, glue or synthetic resins.
Typical wetting, dispersing or emulsifying agents and adjuvants
used in agricultural formulations include, for example, the alkyl
and alkylaryl sulfonates and sulfates and their salts; polyhydric
alcohols; polyethoxylated alcohols, esters and fatty amines; and
other types of surface-active agents, many of which are available
in commerce. The surface-active agent, when used, normally
comprises from 0.1% to 30% by weight of the herbicidal
composition.
Dusts, which are free-flowing admixtures of the active ingredient
with finely divided solids such as talc, clays, flours and other
organic and inorganic solids which act as dispersants and carriers
for the toxicant, are useful formulations for soil-incorporating
application.
Pastes, which are homogeneous suspensions of a finely divided solid
toxicant in a liquid carrier such as water or oil, are employed for
specific purposes. These formulations normally contain about 5% to
about 95% of active ingredient by weight, and may also contain
small amounts of a wetting, dispersing or emulsifying agent to
facilitate dispersion. For application, the pastes are normally
diluted and applied as a spray to the area to be affected.
Other useful formulations for herbicidal applications include
simple solutions of the active ingredient in a dispersant in which
it is completely soluble at the desired concentration, such as
water, acetone, alkylated naphthalenes, xylene and other organic
solvents. Pressurized sprays, typically aerosols, wherein the
active ingredient is dispersed in finely-divided form as a result
of vaporization of a low boiling dispersant solvent carrier, such
as the Freons, may also be used.
The phytotoxic compositions of this invention can be applied to the
plants in the conventional manner. Thus, the dust and liquid
compositions can be applied to the plant by the use of
power-dusters, boom and hand sprayers and spray dusters. The
compositions can also be applied from airplanes as a dust or a
spray or by rope wick applications because they are effective in
very low dosages. In order to modify or control growth of
germinating seeds or emerging seedlings, as a typical example, the
dust and liquid compositions can be applied to the soil according
to conventional methods and can be distributed in the soil to a
depth of at least 1/2 inch below the soil surface. It is not
necessary that the phytotoxic compositions be mechanically admixed
with the soil particles since these compositions can also be
applied merely by spraying or sprinkling the surface of the soil.
The phytotoxic compositions of this invention can also be applied
by addition to irrigation water supplied to the field to be
treated. This method of application permits the penetration of the
compositions into the soil as the water is absorbed therein. Dust
compositions, granular compositions or liquid formulations applied
to the surface of the soil can be distributed below the surface of
the soil by conventional means such as discing, dragging or mixing
operations. In the following examples the herbicidal compound can
be substituted with the herbicidal salt of the compound.
__________________________________________________________________________
General Formula with Ranges Specific Formula
__________________________________________________________________________
EMULSIFIABLE CONCENTRATE FORMULATIONS Herbicidal compound 5-55
herbicidal compound 24 surfactant(s) 5-25 proprietary blend of oil-
10 solvent(s) 20-90 soluble sulfonates and 100% polyoxyethylene
ethers polar solvent 27 petroleum hydrocarbon 39 100% WETTABLE
POWDER FORMULATIONS herbicidal compound 3-90 herbicidal compound 80
wetting agent 0.5-2 sodium dialkyl naphthalene 0.5 dispersing agent
1-8 sulfonate diluent(s) 8.5-87 sodium lignosulfonate 7 100%
attapulgite clay 12.5 100% EXTRUDED GRANULAR FORMULATIONS
herbicidal compound 1-20 herbicidal compound 10 binding agent 0-10
lignin sulfonate 5 diluent(s) 70-99 calcium carbonate 85 100% 100%
FLOWABLE FORMULATIONS herbicidal compound 20-70 herbicidal compound
45 surfactant(s) 1-10 polyoxyethylene ether 5 suspending agent(s)
0.05-1 attagel 0.05 antifreeze agent 1-10 propylene glycol 10
antimicrobial agent 1-10 1,2-benzisothiazoline-3-one 0.03 antifoam
agent 0.1-1 silicone defoamer 0.02 solvent 7.95-77.85 water 39.9
100% 100%
__________________________________________________________________________
When salts are used as the active ingredient in the herbicidal
compositions of this invention it is recommended to use salts that
are agriculturally acceptable.
The phytotoxic compositions of this invention can also contain
other additives, for example, fertilizers, other herbicides and
other pesticides, used as adjuvant or in combination with any of
the above-described adjuvants. Fertilizers useful in combination
with the active ingredients include, for example, ammonium nitrate,
urea and superphosphate.
* * * * *